Azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene

ABSTRACT

An azeotrope-like mixture consisting essentially of chlorotrifluoropropene and at least one component selected from the group consisting of a C 1 -C 3  alcohol, a C 5 -C 6  hydrocarbon, a halogenated hydrocarbon, methylal, methyl acetone, water, nitromethane, and combinations thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part (CIP) of U.S. applicationSer. No. 12/259,694, filed Oct. 28, 2008, and is incorporated herein byreference in its entirety. This application also claims the prioritybenefit of U.S. Provisional Application No. 61/109,007, filed Oct. 28,2008, which is also incorporated herein by reference in its entirety.

BACKGROUND

1. Field of Invention

The present invention relates generally to compositions comprising1-chloro-3,3,3-trifluoropropene. More specifically, the presentinvention provides azeotrope-like compositions comprising1-chloro-3,3,3-trifluoropropene and uses thereof.

2. Description of Related Art

Fluorocarbon based fluids, including chlorofluorocarbons (“CFCs”) orhydrochlorofluorocarbons (“HCFCs”), have properties that are desirablein industrial refrigerants, blowing agents, heat transfer media,solvents, gaseous dielectrics, and other applications. For theseapplications, the use of single component fluids or azeotrope-likemixtures, i.e., those which do not substantially fractionate on boilingand evaporation, are particularly desirable.

Unfortunately, suspected environmental problems, such as global warmingand ozone depletion, have been attributed to the use of some of thesefluids, thereby limiting their contemporary use. Hydrofluoroolefins(“HFOs”) have been proposed as possible replacements for such CFCs,HCFCs, and HFCs. However, the identification of new,environmentally-safe, non-fractionating mixtures comprising HFOs arecomplicated due to the fact that azeotrope formation is not readilypredictable. Therefore, industry is continually seeking new HFO-basedmixtures that are acceptable and environmentally safer substitutes forCFCs, HCFCs, and HFCs. This invention satisfies these needs amongothers.

SUMMARY OF INVENTION

Applicants have discovered that azeotrope-like compositions are formedupon mixing 1-chloro-3,3,3-trifluoropropene (“HFO-1233zd”) with a secondcomponent selected from the group consisting of a C₁-C₃ alcohol, a C₅-C₆hydrocarbon, cyclopentene, a halogenated hydrocarbon selected from1-chloropropane, 2-chloropropane, and 1,1,1,3,3-pentafluorobutane, waterand optionally nitromethane. Preferred azeotrope-like mixtures of theinvention exhibit characteristics which make them particularly desirablefor number of applications, including as refrigerants, as blowing agentsin the manufacture of insulating foams, and as solvents in a number ofcleaning and other applications, including in aerosols and othersprayable compositions. In particular, applicants have recognized thatthese compositions tend to exhibit relatively low global warmingpotentials (“GWPs”), preferably less than about 1000, more preferablyless than about 500, and even more preferably less than about 150.

Accordingly, one aspect of the present invention involves a compositioncomprising a binary azeotrope-like mixture consisting essentially of1-chloro-3,3,3-trifluoropropene and a second component selected from thegroup consisting of a C₁-C₃ alcohol, a C₅-C₆ hydrocarbon, cyclopentene,a halogenated hydrocarbon selected from 1-chloropropane,2-chloropropane, and 1,1,1,3,3-pentafluorobutane, water and optionallynitromethane. In certain preferred embodiments, the composition furthercomprises one or more of the following: co-blowing agent, co-solvent,active ingredient, and additive such as lubricants, stabilizers, metalpassivators, corrosion inhibitors, and flammability suppressants. Incertain preferred embodiments, nitromethane is included in the mixtureas a stabilizer. In certain embodiments, nitromethane also contributesto the azeotrope-like properties of the composition.

Another aspect of the invention provides a blowing agent comprising atleast about 15 wt. % of an azeotrope-like mixture as described herein,and, optionally, co-blowing agents, fillers, vapor pressure modifiers,flame suppressants, and stabilizers.

Another aspect of the invention provides a solvent for use in vapordegreasing, cold cleaning, wiping and similar solvent applicationscomprising an azeotrope-like mixture as described herein.

Another aspect of the invention provides a sprayable compositioncomprising an azeotrope-like mixture as described herein, an activeingredient, and, optionally, inert ingredients and/or solvents andaerosol propellants.

Yet another aspect of the invention provides closed cell foam comprisinga polyurethane-, polyisocyanurate-, or phenolic-based cell wall and acell gas disposed within at least a portion of the cell wall structure,wherein the cell gas comprises the azeotrope-like mixture as describedherein.

According to another embodiment, provided is a polyol premix comprisingthe azeotrope-like mixture described herein.

According to another embodiment, provided is a foamable compositioncomprising the azeotrope-like mixture described herein.

According to another embodiment, provided is a method for producingthermoset foam comprising (a) adding a blowing agent comprising anazeotrope-like composition according to claim 1 to a foamable mixturecomprising a thermosetting resin; (b) reacting said foamable mixture toproduce a thermoset foam; and (c) volatilizing said azeotrope-likecomposition during said reacting.

According to another embodiment, provided is a method for producingthermoplastic foam comprising (a) adding a blowing agent comprising anazeotrope-like composition according to claim 1 to a foamable mixturecomprising a thermoplastic resin; (b) reacting said foamable mixture toproduce a thermoplastic foam; and (c) volatilizing said azeotrope-likecomposition during said reacting.

According to another embodiment, provided is a thermoplastic foam havinga cell wall comprising a thermoplastic polymer and a cell gas comprisingan azeotrope-like mixture as described herein. Preferably, thethermoplastic foam comprises a cell gas having an azeotrope-like mixtureas described herein and having a cell wall constructed of athermoplastic polymer selected from polystyrene, polyethylene,polypropylene, polyvinyl chloride, polytheyeneterephthalate orcombinations thereof.

According to another embodiment, provided is a thermoset foam having acell wall comprising a thermosetting polymer and a cell gas comprisingan azeotrope-like mixture as described herein. Preferably, the thermosetfoam comprises a cell gas having an azeotrope-like mixture as describedherein and a cell wall comprising a thermoset polymer selected frompolyurethane, polyisocyanurate, phenolic, epoxy, or combinationsthereof.

According to another embodiment of the invention, provided is arefrigerant comprising an azeotrope-like mixture as described herein.

DESCRIPTION OF PREFERRED EMBODIMENTS

According to certain embodiments, the present invention providesazeotrope-like compositions comprising, and preferably consistingessentially of, HFO-1233zd and a C₁-C₃ alcohol, a C₅-C₆ hydrocarbon,cyclopentene, a halogenated hydrocarbon selected from 1-chloropropane,2-chloropropane, and 1,1,1,3,3-pentafluorobutane, nitromethane, orwater. Thus, the present invention overcomes the aforementionedshortcomings by providing azeotrope-like compositions that are, inpreferred embodiments, substantially free of CFCs, HCFCs, and HFCs andhave very low global warming potentials have low ozone depletionpotential, and which exhibit relatively constant boiling pointcharacteristics.

As used herein, the term “azeotrope-like” relates to compositions thatare strictly azeotropic or that generally behave like azeotropicmixtures. An azeotropic mixture is a system of two or more components inwhich the liquid composition and vapor composition are equal at thestated pressure and temperature. In practice, this means that thecomponents of an azeotropic mixture are constant-boiling or essentiallyconstant-boiling and generally cannot be thermodynamically separatedduring a phase change. The vapor composition formed by boiling orevaporation of an azeotropic mixture is identical, or substantiallyidentical, to the original liquid composition. Thus, the concentrationof components in the liquid and vapor phases of azeotrope-likecompositions change only minimally, if at all, as the composition boilsor otherwise evaporates. In contrast, boiling or evaporatingnon-azeotropic mixtures changes the component concentrations in theliquid phase to a significant degree.

As used herein, the term “consisting essentially of”, with respect tothe components of an azeotrope-like composition, means the compositioncontains the indicated components in an azeotrope-like ratio, and maycontain additional components provided that the additional components donot form new azeotrope-like systems. For example, azeotrope-likemixtures consisting essentially of two compounds are those that formbinary azeotropes, which optionally may include one or more additionalcomponents, provided that the additional components do not render themixture non-azeotropic and do not form an azeotrope with either or bothof the compounds.

The term “effective amounts” as used herein refers to the amount of eachcomponent which, upon combination with the other component, results inthe formation of an azeotrope-like composition of the present invention.

Unless otherwise specified, the term HFO-1233zd means the cis-isomer,the trans-isomer, or some mixture thereof.

As used herein, the term cis-HFO-1233zd with respect to a component ofan azeotrope-like mixture, means the amount cis-HFO-1233zd relative toall isomers of HFO-1233zd in azeotrope-like compositions is at leastabout 95%, more preferably at least about 98%, even more preferably atleast about 99%, even more preferably at least about 99.9%. In certainpreferred embodiments, the cis-HFO-1233zd component in azeotrope-likecompositions of the present invention is essentially purecis-HFO-1233zd.

As used herein, the term trans-HFO-1233zd with respect to a component ofan azeotrope-like mixture, means the amount trans-HFO-1233zd relative toall isomers of HFO-1233zd in azeotrope-like compositions is at leastabout 95%, more preferably at least about 98%, even more preferably atleast about 99%, even more preferably at least about 99.9%. In certainpreferred embodiments, the trans-HFO-1233zd component in azeotrope-likecompositions of the present invention is essentially puretrans-HFO-1233zd.

As used herein, the term “ambient pressure” with respect to boilingpoint data means the atmospheric pressure surrounding the relevantmedium. In general, ambient pressure is 14.7 psia, but could vary +/−0.5psi.

The azeotrope-like compositions of the present invention can be producedby combining effective amounts of HFO-1233zd with one or more othercomponents, preferably in fluid form. Any of a wide variety of methodsknown in the art for combining two or more components to form acomposition can be adapted for use in the present methods. For example,HFO-1233zd and methanol can be mixed, blended, or otherwise combined byhand and/or by machine, as part of a batch or continuous reaction and/orprocess, or via combinations of two or more such steps. In light of thedisclosure herein, those of skill in the art will be readily able toprepare azeotrope-like compositions according to the present inventionwithout undue experimentation.

Fluoropropenes, such as CF₃CCl═CH₂, can be produced by known methodssuch as catalytic vapor phase fluorination of various saturated andunsaturated halogen-containing C3 compounds, including the methoddescribed in U.S. Pat. Nos. 2,889,379; 4,798,818 and 4,465,786, each ofwhich is incorporated herein by reference.

EP 974,571, also incorporated herein by reference, discloses thepreparation of 1,1,1,3-chlorotrifluoropropene by contacting1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with achromium based catalyst at elevated temperature, or in the liquid phasewith an alcoholic solution of KOH, NaOH, Ca(OH)2 or Mg(OH)2. The endproduct is approximately 90% by weight of the trans isomer and 10% byweight cis. Preferably, the cis isomers are substantially separated fromthe trans forms so that the resultant preferred form of1-chloro-3,3,3-trifluoropropene is more enriched in the cis isomer.Because the cis isomer has a boiling point of about 40° C. in contrastwith the trans isomer boiling point of about 20° C., the two can easilybe separated by any number of distillation methods known in the art.However, a preferred method is batch distillation. According to thismethod, a mixture of cis and trans 1-chloro-3,3,3-trifluoropropene ischarged to the reboiler. The trans isomer is removed in the overheadleaving the cis isomer in the reboiler. The distillation can also be runin a continuous distillation where the trans isomer is removed in theoverhead and the cis isomer is removed in the bottom. This distillationprocess can yield about 99.9+% puretrans-1-chloro-3,3,3-trifluoropropene and 99.9+%cis-1-chloro-3,3,3-trifluoropropene.

In a preferred embodiments, the azeotrope-like composition compriseseffective amounts of HFO-1233zd and a C₁-C₃ alcohol. Preferably, theC₁-C₃ alcohol is selected from the group consisting of methanol,ethanol, and isopropanol. In certain preferred embodiments, theHFO-1233zd is trans-HFO-1233zd. In certain other embodiments, theHFO-1233zd is cis-HFO-1233zd.

Cis-HFO-1233zd/Methanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of cis-HFO-1233zd and methanol. More preferably, thesebinary azeotrope-like compositions consist essentially of about 78 toabout 99.9 wt. % cis-HFO-1233zd and from about 0.1 to about 22 wt. %methanol, more preferably from about 85 to about 99.9 wt. %cis-HFO-1233zd and about 0.1 to about 15 wt. % methanol, and even morepreferably from about 88 to about 99.5 wt. % cis-HFO-1233zd and fromabout 0.5 to about 12 wt. % methanol.

Preferably, the cis-HFO-1233zd/methanol compositions of the presentinvention have a boiling point of about 35.2±1° C. at ambient pressure(Ambient pressure need to be defined)

Trans-HFO-1233zd/Methanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and methanol. More preferably,these binary azeotrope-like compositions consist essentially of about 70to about 99.95 wt. % trans-HFO-1233zd and from about 0.05 to about 30wt. % methanol, more preferably from about 90 to about 99.95 wt. %trans-HFO-1233zd and about 0.05 to about 10 wt. % methanol, and evenmore preferably from about 95 to about 99.95 wt. % trans-HFO-1233zd andfrom about 0.05 to about 5 wt. % methanol.

Preferably, the trans-HFO-1233zd/methanol compositions of the presentinvention have a boiling point of from about 17° C. to about 19° C.,more preferably about 17° C. to about 18° C., even more preferably about17° C. to about 17.5° C., and most preferably about 17.15° C.±1° C., allmeasured at ambient pressure.

Cis-HFO-1233zd/Ethanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of cis-HFO-1233zd and ethanol. More preferably, thesebinary azeotrope-like compositions consist essentially of about 65 toabout 99.9 wt. % cis-HFO-1233zd and from about 0.1 to about 35 wt. %ethanol, more preferably from about 79 to about 99.9 wt. %cis-HFO-1233zd and about 0.1 to about 21 wt. % ethanol, and even morepreferably from about 88 to about 99.5 wt. % cis-HFO-1233zd and fromabout 0.5 to about 12 wt. % ethanol.

Preferably, the cis-HFO-1233zd/ethanol compositions of the presentinvention have a normal boiling point of about 37.4° C.±1° C. at ambientpressure.

Trans-HFO-1233zd/Ethanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and ethanol. More preferably,these binary azeotrope-like compositions consist essentially of about 85to about 99.9 wt. % trans-HFO-1233zd and from about 0.1 to about 15 wt.% ethanol, more preferably from about 92 to about 99.9 wt. %trans-HFO-1233zd and about 0.1 to about 8 wt. % ethanol, and even morepreferably from about 96 to about 99.9 wt. % trans-HFO-1233zd and fromabout 0.1 to about 4 wt. % ethanol.

Preferably, the trans-HFO-1233zd/ethanol compositions of the presentinvention have a normal boiling point of about 18.1° C.±1° C. at ambientpressure.

Cis-HFO-1233zd/Isopropanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of cis-HFO-1233zd and isopropanol. More preferably,these binary azeotrope-like compositions consist essentially of about 85to about 99.99 wt. % cis-HFO-1233zd and from about 0.01 to about 15 wt.% isopropanol, more preferably from about 88 to about 99.99 wt. %cis-HFO-1233zd and about 0.01 to about 12 wt. % isopropanol, and evenmore preferably from about 92 to about 99.5 wt. % cis-HFO-1233zd andfrom about 0.5 to about 8 wt. % isopropanol.

Preferably, the cis-HFO-1233zd/isopropanol compositions of the presentinvention have a normal boiling point of about 38.1° C.±1° C. at ambientpressure.

Trans-HFO-1233zd/Isopropanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and isopropanol. More preferably,these binary azeotrope-like compositions consist essentially of about 90to about 99.9 wt. % trans-HFO-1233zd and from about 0.1 to about 10 wt.% isopropanol, more preferably from about 94 to about 99.9 wt. %trans-HFO-1233zd and about 0.1 to about 6 wt. % isopropanol, and evenmore preferably from about 95 to about 99.9 wt. % trans-HFO-1233zd andfrom about 0.1 to about 5 wt. % isopropanol.

Preferably, the trans-HFO-1233zd/isopropanol compositions of the presentinvention have a normal boiling point of about 17.9° C.±1° C. at ambientpressure.

In a preferred embodiments, the azeotrope-like composition compriseseffective amounts of HFO-1233zd and a C₅-C₆ hydrocarbon. Preferably, theC₅-C₆ hydrocarbon is selected from the group consisting of n-pentane,isopentane, neopentane, cyclopentane, cyclopentene, n-hexane, andisohexane. In certain preferred embodiments, the HFO-1233zd istrans-HFO-1233zd. In certain other embodiments, the HFO-1233zd iscis-HFO-1233zd.

Trans-HFO-1233zd/n-Pentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and n-pentane. More preferably,these binary azeotrope-like compositions consist essentially of about 65to about 99.95 wt. % trans-HFO-1233zd and from about 0.05 to about 35wt. % n-pentane, more preferably from about 84 to about 99.9 wt. %trans-HFO-1233zd and about 0.1 to about 16 wt. % n-pentane, and evenmore preferably from about 92 to about 99.5 wt. % trans-HFO-1233zd andfrom about 0.5 to about 8 wt. % n-pentane.

Preferably, the trans-HFO-1233zd/n-pentane compositions of the presentinvention have a boiling point of from about 17° C. to about 19° C.,more preferably about 17° C. to about 18° C., even more preferably about17.3° C. to about 17.6° C., and most preferably about 17.4° C.±1° C.,all measured at ambient pressure.

Cis-HFO-1233zd/n-Pentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of cis-HFO-1233zd and n-pentane. More preferably,these binary azeotrope-like compositions consist essentially of about 20to about 99.5 wt. % cis-HFO-1233zd and from about 0.5 to about 80 wt. %n-pentane, more preferably from about 50 to about 99.5 wt. %cis-HFO-1233zd and about 0.5 to about 50 wt. % n-pentane, and even morepreferably from about 60 to about 99.5 wt. % cis-HFO-1233zd and fromabout 0.5 to about 40 wt. % n-pentane.

Preferably, the cis-HFO-1233zd/n-pentane compositions of the presentinvention have a normal boiling point of about 35° C.±1° C. at ambientpressure.

Trans-HFO-1233zd/Isopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and isopentane. More preferably,these binary azeotrope-like compositions consist essentially of about 60to about 99.95 wt. % trans-HFO-1233zd and from about 0.05 to about 40wt. % isopentane, more preferably from about 70 to about 95 wt. %trans-HFO-1233zd and about 5 to about 30 wt. % isopentane, and even morepreferably from about 80 to about 90 wt. % trans-HFO-1233zd and fromabout 10 to about 20 wt. % isopentane.

Preferably, the trans-HFO-1233zd/isopentane compositions of the presentinvention have a boiling of from about 15° C. to about 18° C., morepreferably about 16° C. to about 17° C., even more preferably about16.7° C. to about 16.9° C., and most preferably about 16.8° C.±1° C.,all measured at ambient pressure.

Trans-HFO-1233zd/Neopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and neopentane. More preferably,these binary azeotrope-like compositions consist essentially of about 5to about 70 wt. % trans-HFO-1233zd and from about 30 to about 95 wt. %neopentane, more preferably from about 15 to about 55 wt. %trans-HFO-1233zd and about 45 to about 85 wt. % neopentane, and evenmore preferably from about 20 to about 50 wt. % trans-HFO-1233zd andfrom about 50 to about 80 wt. % neopentane.

Preferably, the trans-HFO-1233zd/neopentane compositions of the presentinvention have a boiling of from about 7.7° C. to about 8.4° C., morepreferably about 7.7° C. to about 8.0° C., and most preferably about7.7° C.±1° C., all measured at ambient pressure.

Cis-HFO-1233zd/Neopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of cis-HFO-1233zd and neopentane. More preferably,these binary azeotrope-like compositions consist essentially of about 5to about 50 wt. % cis-HFO-1233zd and from about 50 to about 95 wt. %neopentane, more preferably from about 20 to about 45 wt. %cis-HFO-1233zd and about 55 to about 80 wt. % neopentane, and even morepreferably from about 30 to about 40 wt. % cis-HFO-1233zd and from about60 to about 70 wt. % neopentane.

Preferably, the cis-HFO-1233zd/neopentane compositions of the presentinvention have a normal boiling point of about 8° C.±1° C.

Trans-HFO-1233zd/Cyclopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and cyclopentane. More preferably,these binary azeotrope-like compositions consist essentially of about 95to about 99.9 wt. % trans-HFO-1233zd and from about 0.1 to about 5 wt. %cyclopentane, more preferably from about 97 to about 99.9 wt. %trans-HFO-1233zd and about 0.1 to about 3 wt. % cyclopentane, and evenmore preferably from about 98 to about 99.9 wt. % trans-HFO-1233zd andfrom about 2 to about 98 wt. % cyclopentane.

Preferably, the trans-HFO-1233zd/cyclopentane compositions of thepresent invention have a normal boiling point of about 17.5° C.±1° C. atambient pressure.

Cis-HFO-1233zd/Cyclopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of cis-HFO-1233zd and cyclopentane. More preferably,these binary azeotrope-like compositions consist essentially of about 42to about 99 wt. % cis-HFO-1233zd and from about 1 to about 58 wt. %cyclopentane, more preferably from about 50 to about 95 wt. %cis-HFO-1233zd and about 5 to about 50 wt. % cyclopentane, and even morepreferably from about 60 to about 93 wt. % cis-HFO-1233zd and from about7 to about 40 wt. % cyclopentane.

Preferably, the cis-HFO-1233zd/cyclopentane compositions of the presentinvention have a normal boiling point of about 34.7° C.±1° C. at ambientpressure.

Trans-HFO-1233zd/Cyclopentene Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and cyclopentene. More preferably,these binary azeotrope-like compositions consist essentially of about 95to about 99.9 wt. % trans-HFO-1233zd and from about 0.1 to about 5 wt. %cyclopentene, more preferably from about 97 to about 99.9 wt. %trans-HFO-1233zd and about 0.1 to about 3 wt. % cyclopentene, and evenmore preferably from about 98 to about 99.9 wt. % trans-HFO-1233zd andfrom about 2 to about 98 wt. % cyclopentene.

Preferably, the trans-HFO-1233zd/cyclopentene compositions of thepresent invention have a normal boiling point of about 18.1° C.±1° C. atambient pressure.

Trans-HFO-1233zd/n-Hexane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and n-hexane. More preferably,these binary azeotrope-like compositions consist essentially of about 95to about 99.99 wt. % trans-HFO-1233zd and from about 0.01 to about 5 wt.% n-hexane, more preferably from about 97 to about 99.99 wt. %trans-HFO-1233zd and about 0.01 to about 3 wt. % n-hexane, and even morepreferably from about 97.2 to about 99.99 wt. % trans-HFO-1233zd andfrom about 0.01 to about 2.8 wt. % n-hexane.

Preferably, the trans-HFO-1233zd/n-hexane compositions of the presentinvention have a normal boiling point of about 17.4° C.±1° C. at ambientpressure.

Cis-HFO-1233zd/n-Hexane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of cis-HFO-1233zd and n-hexane. More preferably, thesebinary azeotrope-like compositions consist essentially of about 80 toabout 99.5 wt. % cis-HFO-1233zd and from about 0.5 to about 20 wt. %n-hexane, more preferably from about 90 to about 99.5 wt. %cis-HFO-1233zd and about 0.5 to about 10 wt. % n-hexane, and even morepreferably from about 95 to about 99.5 wt. % cis-HFO-1233zd and fromabout 0.5 to about 5 wt. % n-hexane.

Preferably, the cis-HFO-1233zd/n-hexane compositions of the presentinvention have a normal boiling point of about 39° C.±1° C. at ambientpressure.

Trans-HFO-1233zd/Isohexane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and isohexane. More preferably,these binary azeotrope-like compositions consist essentially of about94.4 to about 99.99 wt. % trans-HFO-1233zd and from about 0.01 to about5.6 wt. % isohexane, more preferably from 96 wt. % to about 99.99 wt. %trans-HFO-1233zd and about 0.01 to about 4 wt. % isohexane, and evenmore preferably from about 97 to about 99.99 wt. % trans-HFO-1233zd andfrom about 0.01 to about 3 wt. % isohexane.

Preferably, the trans-HFO-1233zd/isohexane compositions of the presentinvention have a boiling point of from about 17° C. to about 19° C.,more preferably about 17° C. to about 18° C., even more preferably about17.3° C. to about 17.6° C., and most preferably about 17.4° C.±1° C.,all measured at ambient pressure.

Cis-HFO-1233zd/Isohexane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of cis-HFO-1233zd and isohexane. More preferably,these binary azeotrope-like compositions consist essentially of about 70to about 99.5 wt. % cis-HFO-1233zd and from about 0.5 to about 30 wt. %isohexane, more preferably from 85 wt. % to about 99.5 wt. %cis-HFO-1233zd and about 0.5 to about 15 wt. % isohexane, and even morepreferably from about 93 to about 99.5 wt. % cis-HFO-1233zd and fromabout 0.5 to about 7 wt. % isohexane.

Preferably, the cis-HFO-1233zd/isohexane compositions of the presentinvention have a normal boiling point of about 37° C.±1° C.

In a preferred embodiments, the azeotrope-like composition compriseseffective amounts of HFO-1233zd and a hydrohalocarbon. Preferably, thehydrohalocarbon is selected from the group consisting of1-chloropropane, 2-chloropropane, 1,1,1,3,3-pentafluorobutane(HFC-365mfc), and trans-1,2-dichloroethylene (trans-1,2-DCE). In certainpreferred embodiments, the HFO-1233zd is trans-HFO-1233zd. In certainother embodiments, the HFO-1233zd is cis-HFO-1233zd.

Trans-HFO-1233zd/1-Chloropropane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and 1-chloropropane. Morepreferably, these binary azeotrope-like compositions consist essentiallyof about 96 to about 99.9 wt. % trans-HFO-1233zd and from about 0.1 toabout 4 wt. % 1-chloropropane, more preferably from about 98 to about99.9 wt. % trans-HFO-1233zd and about 0.1 to about 2 wt. %1-chloropropane, and even more preferably from about 99 to about 99.9wt. % trans-HFO-1233zd and from about 0.1 to about 1 wt. %1-chloropropane.

Preferably, the trans-HFO-1233zd/1-chloropropane compositions of thepresent invention have a normal boiling point of about 18° C.±1° C. atambient pressure.

Trans-HFO-1233zd/2-Chloropropane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and 2-chloropropane. Morepreferably, these binary azeotrope-like compositions consist essentiallyof about 94 to about 99.9 wt. % trans-HFO-1233zd and from about 0.1 toabout 6 wt. % 2-chloropropane, more preferably from about 97 to about99.9 wt. % trans-HFO-1233zd and about 0.1 to about 3 wt. %2-chloropropane, and even more preferably from about 99 to about 99.9wt. % trans-HFO-1233zd and from about 0.1 to about 1 wt. %2-chloropropane.

Preferably, the trans-HFO-1233zd/2-chloropropane compositions of thepresent invention have a normal boiling point of about 17.8° C.±1° C. atambient pressure.

Trans-HFO-1233zd/HFC-365mfc Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and HFC-365mfc. More preferably,these binary azeotrope-like compositions consist essentially of about 89to about 99.9 wt. % trans-HFO-1233zd and from about 0.1 to about 11 wt.% HFC-365mfc, more preferably from about 92.5 to about 99.9 wt. %trans-HFO-1233zd and about 0.1 to about 7.5 wt. % HFC-365mfc, and evenmore preferably from about 95 to about 99.9 wt. % trans-HFO-1233zd andfrom about 0.1 to about 5 wt. % HFC-365mfc.

Trans-HFO-1233zd/trans-1,2-DCE Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and trans-1,2-DCE. Morepreferably, these binary azeotrope-like compositions consist essentiallyof about 60 to about 99.99 wt. % trans-HFO-1233zd and from about 0.01 toabout 40 wt. % trans-1,2-DCE, more preferably from about 75 to about99.99 wt. % trans-HFO-1233zd and about 0.01 to about 25 wt. %trans-1,2-DCE, and even more preferably from about 95 weight percent toabout 99.99 wt % trans-HFO-1233zd and from about 0.01 to about 5 wt. %trans-1,2-DCE.

Preferably, the trans-HFO-1233zd/trans-1,2-DCE compositions of thepresent invention have a boiling of from about 17° C. to about 19° C.,more preferably about 17.5° C. to about 18.5° C., even more preferablyabout 17.5° C. to about 18° C., and most preferably about 17.8° C.±1°C., all measured at ambient pressure.

Cis-HFO-1233zd/trans-1,2-DCE Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of cis-HFO-1233zd and trans-1,2-DCE. More preferably,these binary azeotrope-like compositions consist essentially of about 42to about 99.9 wt. % cis-HFO-1233zd and from about 0.1 to about 58 wt. %trans-1,2-DCE, more preferably from about 55 to about 99.5 wt. %cis-HFO-1233zd and about 0.5 to about 45 wt. % trans-1,2-DCE, and evenmore preferably from about 65 weight percent to about 99 wt %cis-HFO-1233zd and from about 1 to about 35 wt. % trans-1,2-DCE.

Preferably, the cis-HFO-1233zd/trans-1,2-DCE compositions of the presentinvention have a boiling point of about 37.0° C.±1° C. at ambientpressure.

Trans-HFO-1233zd/methylal Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and methylal. More preferably,these binary azeotrope-like compositions consist essentially of about 95to about 99.9 wt. % trans-HFO-1233zd and from about 0.1 to about 5 wt. %methylal, more preferably from about 97 to about 99.9 wt. %trans-HFO-1233zd and about 0.1 to about 3 wt. % methylal, and even morepreferably from about 98.5 weight percent to about 99.9 wt %trans-HFO-1233zd and from about 0.1 to about 1.5 wt. % methylal.

Preferably, the trans-HFO-1233zd/methylal compositions of the presentinvention have a normal boiling point of about 17.3° C.±1° C. at ambientpressure.

Trans-HFO-1233zd/methyl acetate Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and methyl acetate. Morepreferably, these binary azeotrope-like compositions consist essentiallyof about 90 to about 99.9 wt. % trans-HFO-1233zd and from about 0.1 toabout 10 wt. % methyl acetate, more preferably from about 95 to about99.9 wt. % trans-HFO-1233zd and about 0.1 to about 5 wt. % methylacetate, and even more preferably from about 98.5 weight percent toabout 99.9 wt % trans-HFO-1233zd and from about 0.1 to about 1.5 wt. %methyl acetate.

Preferably, the trans-HFO-1233zd/methyl acetate compositions of thepresent invention have a normal boiling point of about 17.5° C.±1° C. atambient pressure.

Trans-HFO-1233zd/water Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and water. More preferably, thesebinary azeotrope-like compositions consist essentially of about 70 toabout 99.95 wt. % trans-HFO-1233zd and from about 0.05 to about 30 wt. %water, more preferably from about 86 to about 99.95 wt. %trans-HFO-1233zd and about 0.05 to about 14 wt. % water, and mostpreferably about 90 to about 99.95 wt. % trans-HFO-1233zd and about 0.05to about 10 wt. % water.

Preferably, the trans-HFO-1233zd/water compositions of the presentinvention have a boiling point of about 17.4° C.±1° C. at ambientpressure.

Trans-HFO-1233zd/Nitromethane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd and nitromethane. More preferably,these binary azeotrope-like compositions consist essentially of about 98to about 99.99 wt. % trans-HFO-1233zd and from about 0.01 to about 2 wt.% nitromethane, more preferably from about 99 to about 99.99 wt. %trans-HFO-1233zd and about 0.01 to about 1 wt. % nitromethane, and evenmore preferably from about 99.9 to about 99.99 wt. % trans-HFO-1233zdand from about 0.01 to about 0.1 wt. % nitromethane.

Preferably, the trans-HFO-1233zd/nitromethane compositions of thepresent invention have a normal boiling point of about 17.4° C.±1° C. atambient pressure.

Cis-HFO-1233zd/Nitromethane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of cis-HFO-1233zd and nitromethane. More preferably,these binary azeotrope-like compositions consist essentially of about 95to about 99.9 wt. % cis-HFO-1233zd and from about 0.1 to about 5 wt. %nitromethane, more preferably from about 97 to about 99.9 wt. %cis-HFO-1233zd and about 0.1 to about 3 wt. % nitromethane, and evenmore preferably from about 99 to about 99.9 wt. % cis-HFO-1233zd andfrom about 0.1 to about 1 wt. % nitromethane.

Preferably, the cis-HFO-1233zd/nitromethane compositions of the presentinvention have a normal boiling point of about 39° C.±1° C. at ambientpressure.

Trans-HFO-1233zd/trans-1,2-DCE/Methanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd, methanol, and trans-1,2-DCE. Morepreferably, these ternary azeotrope-like compositions consistessentially of about 80 to about 99.9 wt. % trans-HFO-1233zd, from about0.05 to about 15 wt. % methanol, and from about 0.05 to about 10 wt. %trans-1,2-DCE, even more preferably from about 90 to about 99.9 wt. %trans-HFO-1233zd, from about 0.05 to about 9 wt. % methanol, and about0.05 to about 5 wt. % trans-1,2-DCE, and most preferably from about 95to about 99.9 wt. % trans-HFO-1233zd, from about 0.05 to about 5 wt. %methanol, and from about 0.05 to about 3 wt. % trans-1,2-DCE.

Preferably, the trans-HFO-1233zd/methanol/trans-1,2-DCE compositions ofthe present invention have a boiling point of from about 16.6° C.±1° C.at ambient pressure

Trans-HFO-1233zd/Methanol/n-Pentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-HFO-1233zd, methanol, and n-pentane. Morepreferably, these ternary azeotrope-like compositions consistessentially of about 55 to about 99.90 wt. % trans-HFO-1233zd, fromabout 0.05 to about 10 wt. % methanol, and from about 0.05 to about 35wt. % n-pentane, even more preferably from about 79 to about 98 wt. %trans-HFO-1233zd, from about 0.1 to about 5 wt. % methanol, and about1.9 to about 16 wt. % n-pentane, and most preferably from about 88 toabout 96 wt. % trans-HFO-1233zd, from about 0.5 to about 4 wt. %methanol, and from about 3.5 to about 8 wt. % n-pentane.

Preferably, the trans-HFO-1233zd/methanol/n-pentane compositions of thepresent invention have a boiling point of from about 17° C. to about 19°C., more preferably about 17° C. to about 18° C., even more preferablyabout 17.1° C. to about 17.6° C., and most preferably about 17.4° C.±1°C., all measured at a pressure of about 14 psia.

The azeotrope-like compositions of the present invention may furtherinclude a variety of optional additives including, but not limited to,lubricants, stabilizers, metal passivators, corrosion inhibitors,flammability suppressants, and the like. Examples of suitablestabilizers include diene-based compounds, and/or phenol compounds,and/or epoxides selected from the group consisting of aromatic epoxides,alkyl epoxides, alkenyl epoxides, and combinations of two or morethereof. Preferably, these optional additives do not affect the basicazeotrope-like characteristic of the composition.

Blowing Agents:

In another embodiment of the invention, provided are blowing agentscomprising at least one azeotrope-like mixture described herein. Polymerfoams are generally of two general classes: thermoplastic foams andthermoset foams.

Thermoplastic foams are produced generally via any method known in theart, including those described in Throne, Thermoplastic Foams, 1996,Sherwood Publishers, Hinkley, Ohio, or Klempner and Sendijarevic,Polymeric Foams and Foam Technology, 2^(nd) Edition 2004, Hander GardnerPublications. Inc, Cincinnati, Ohio. For example, extruded thermoplasticfoams can be prepared by an extrusion process whereby a solution ofblowing agent in molten polymer, formed in an extruder under pressure,is forced through an orifice onto a moving belt at ambient temperatureor pressure or optionally at reduced pressure to aid in foam expansion.The blowing agent vaporizes and causes the polymer to expand. Thepolymer simultaneously expands and cools under conditions that give itenough strength to maintain dimensional stability at the timecorresponding to maximum expansion. Polymers used for the production ofextruded thermoplastic foams include, but are not limited to,polystyrene, polyethylene (HDPE, LDPE, and LLDPE), polypropylene,polyethylene terephthalate, ethylene vinyl acetate, and mixturesthereof. A number of additives are optionally added to the moltenpolymer solution to optimize foam processing and properties including,but not limited to, nucleating agents (e.g., talc), flame retardants,colorants, processing aids (e.g., waxes), cross linking agents,permeability modifiers, and the like. Additional processing steps suchas irradiation to increase cross linking, lamination of a surface filmto improve foam skin quality, trimming and planning to achieve foamdimension requirements, and other processes may also be included in themanufacturing process.

In general, the blowing agent may include the azeotrope-likecompositions of the present invention in widely ranging amounts. It isgenerally preferred, however, that the blowing agents comprise at leastabout 15% by weight of the blowing agent. In certain preferredembodiments, the blowing agent comprises at least about 50% by weight ofthe present compositions, and in certain embodiments the blowing agentconsists essentially of the present azeotrope-like composition. Incertain preferred embodiments, the blowing agent includes, in additionto the present azeotrope-like mixtures, one or more co-blowing agents,fillers, vapor pressure modifiers, flame suppressants, stabilizers, andlike adjuvants.

In certain preferred embodiments, the blowing agent is characterized asa physical (i.e., volatile) blowing agent comprising the azeotrope-likemixture of the present invention. In general, the amount of blowingagent present in the blended mixture is dictated by the desired foamdensities of the final foams products and by the pressure and solubilitylimits of the process. For example, the proportions of blowing agent inparts by weight can fall within the range of about 1 to about 45 parts,more preferably from about 4 to about 30 parts, of blowing agent per 100parts by weight of polymer. The blowing agent may comprise additionalcomponents mixed with the azeotrope-like composition, includingchlorofluorocarbons such as trichlorofluoromethane (CFC-11),dichlorodifluoromethane (CFC-12), hydrochlorofluorocarbons such as1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane(HCFC-142b), chlorodifluoromethane (HCFC-22), hydrofluorocarbons such as1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a),1,1,1,3,3-pentafluoropropane (HFC-245fa), and1,1,1,3,3-pentafluorobutane (HFC-365mfc), hydrocarbons such as propane,butane, isobutane, cyclopentane, carbon dioxide, chlorinatedhydrocarbons alcohols, ethers, ketones and mixtures thereof.

In certain embodiments, the blowing agent is characterized as a chemicalblowing agent. Chemical blowing agents are materials that, when exposedto temperature and pressure conditions in the extruder, decompose toliberate a gas, generally carbon dioxide, carbon monoxide, nitrogen,hydrogen, ammonia, nitrous oxide, of mixtures thereof. The amount ofchemical blowing agent present is dependent on the desired final foamdensity. The proportions in parts by weight of the total chemicalblowing agent blend can fall within the range of from less than 1 toabout 15 parts, preferably from about 1 to about 10 parts, of blowingagent per 100 parts by weight of polymer.

In certain preferred embodiments, dispersing agents, cell stabilizers,surfactants and other additives may also be incorporated into theblowing agent compositions of the present invention. Surfactants areoptional, but preferably are added to serve as cell stabilizers. Somerepresentative materials are sold under the names of DC-193, B-8404, andL-5340 which are, generally, polysiloxane polyoxyalkylene blockco-polymers such as those disclosed in U.S. Pat. Nos. 2,834,748,2,917,480, and 2,846,458, each of which are incorporated herein byreference. Other optional additives for the blowing agent mixtureinclude flame retardants or suppressants such astri(2-chloroethyl)phosphate, tri(2-chloropropyl)phosphate,tri(2,3-dibromopropyl)-phosphate, tri(1,3-dichloropropyl) phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminum trihydrate, polyvinyl chloride, and the like. Withrespect to thermoset foams, in general any thermoset polymer can beused, including but not limited to polyurethane, polyisocyanurate,phenolic, epoxy, and combinations thereof. In general these foams areproduced by bringing together chemically reactive components in thepresence of one or more blowing agents, including the azeotrope-likecomposition of this invention and optionally other additives, includingbut not limited to cell stabilizers, solubility enhancers, catalysts,flame retardants, auxiliary blowing agents, inert fillers, dyes, and thelike. With respect to the preparation of polyurethane orpolyisocyanurate foams using the azeotrope like compositions describedin the invention, any of the methods well known in the art can beemployed, see Saunders and Frisch, Volumes I and II PolyurethanesChemistry and Technology (1962) John Wiley and Sons, New York, N.Y. Ingeneral, polyurethane or polyisocyanurate foams are prepared bycombining an isocyanate, a polyol or mixture of polyols, a blowing agentor mixture of blowing agents, and other materials such as catalysts,surfactants, and optionally, flame retardants, colorants, or otheradditives.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in preblended formulations. Mosttypically, the foam formulation is preblended into two components. Theisocyanate and optionally certain surfactants and blowing agentscomprise the first component, commonly referred to as the “A” component.The polyol or polyol mixture, surfactant, catalysts, blowing agents,flame retardant, and other isocyanate reactive components comprise thesecond component, commonly referred to as the “B” component.Accordingly, polyurethane or polyisocyanurate foams are readily preparedby bringing together the A and B side components either by hand mix forsmall preparations and, preferably, machine mix techniques to formblocks, slabs, laminates, pour-in-place panels and other items, sprayapplied foams, froths, and the like. Optionally, other ingredients suchas fire retardants, colorants, auxiliary blowing agents, water, and evenother polyols can be added as a third stream to the mix head or reactionsite. Most conveniently, however, they are all incorporated into one BComponent as described above.

Any organic polyisocyanate can be employed in polyurethane orpolyisocyanurate foam synthesis inclusive of aliphatic and aromaticpolyisocyanates. Preferred as a class are the aromatic polyisocyanates.Typical aliphatic polyisocyanates are alkylene diisocyanates such astri, tetra, and hexamethylene diisocyanate, isophorene diisocyanate,4,4′-methylenebis(cyclohexyl isocyanate), and the like; typical aromaticpolyisocyanates include m-, and p-phenylene diisocyanate, polymethylenepolyphenyl isocyanate, 2,4- and 2,6-toluenediisocyanate, dianisidinediisocyanate, bitoylene isocyanate, naphthylene 1,4-diisocyanate,bis(4-isocyanatophenyl)methene, bis(2-methyl-4-isocyanatophenyl)methane,and the like.

Preferred polyisocyanates are the polymethylene polyphenyl isocyanates,particularly the mixtures containing from about 30 to about 85 percentby weight of methylenebis(phenyl isocyanate) with the remainder of themixture comprising the polymethylene polyphenyl polyisocyanates offunctionality higher than 2.

Typical polyols used in the manufacture of polyurethane foams include,but are not limited to, aromatic amino-based polyether polyols such asthose based on mixtures of 2,4- and 2,6-toluenediamine condensed withethylene oxide and/or propylene oxide. These polyols find utility inpour-in-place molded foams. Another example is aromatic alkylamino-basedpolyether polyols such as those based on ethoxylated and/or propoxylatedaminoethylated nonylphenol derivatives. These polyols generally findutility in spray applied polyurethane foams. Another example issucrose-based polyols such as those based on sucrose derivatives and/ormixtures of sucrose and glycerine derivatives condensed with ethyleneoxide and/or propylene oxide.

Examples of polyols used in polyurethane modified polyisocyanurate foamsinclude, but are not limited to, aromatic polyester polyols such asthose based on complex mixtures of phthalate-type or terephthalate-typeesters formed from polyols such as ethylene glycol, diethylene glycol,or propylene glycol. These polyols are used in rigid laminatedboardstock, can be blended with other types of polyols such as sucrosebased polyols, and used in other polyurethane foam applications such asdescribed above.

Catalysts used in the manufacture of polyurethane foams are typicallytertiary amines including, but not limited to, N-alkylmorpholines,N-alkylalkanolamines, N,N-dialkylcyclohexylamines, and alkylamines wherethe alkyl groups are methyl, ethyl, propyl, butyl, and the like andisomeric forms thereof; and hetrocyclic amines. Typical, but notlimiting examples are triethylenediamine, tetramethylethylenediamine,bis(2-dimethylaminoethyl)ether, triethylamine, tripropylamine,tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine,piperazine, N,N-dimethylcyclohexylamine, N-ethylmorpholine,2-methylpiperazine, N,N-dimethylethanolamine, tetramethylpropanediamine,methyltriethylenediamine, and the like, and mixtures thereof.

Optionally, non-amine polyurethane catalysts are used. Typical of suchcatalysts are organometallic compounds of bismuth, lead, tin, titanium,antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc,nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium, andthe like. Included as illustrative are bismuth nitrate, lead2-ethylhexoate, lead benzoate, ferric chloride, antimony trichloride andantimony glycolate. A preferred organo-tin class includes the stannoussalts of carboxylic acids such as stannous octoate, stannous2-ethylhexoate, stannous laurate, and the like, as well as dialkyl tinsalts of carboxylic acids such as dibutyl tin diacetate, dibutyl tindilaurate, dioctyl tin diacetate, and the like.

In the preparation of polyisocyanurate foams, trimerization catalystsare used for the purpose of converting the blends in conjunction withexcess A component to polyisocyanurate-polyurethane foams. Thetrimerization catalysts employed can be any catalyst known to oneskilled in the art, including, but not limited to, glycine salts andtertiary amine trimerization catalysts and alkali metal carboxylic acidsalts and mixtures of the various types of catalysts. Preferred specieswithin the classes are potassium acetate, potassium octoate, andN-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

Dispersing agents, cell stabilizers, and surfactants can be incorporatedinto the present blends. Surfactants, which are, generally, polysiloxanepolyoxyalkylene block co-polymers, such as those disclosed in U.S. Pat.Nos. 2,834,748, 2,917,480, and 2,846,458, which are incorporated hereinby reference.

Other optional additives for the blends can include flame retardantssuch as tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate,tris(2,3-dibromopropyl)phosphate, tris(1,3-dichloropropyl)phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminum trihydrate, polyvinyl chloride, and the like. Otheroptional ingredients can include from 0 to about 3 percent water, whichchemically reacts with the isocyanate to produce carbon dioxide. Thiscarbon dioxide acts as an auxiliary blowing agent.

Also included in the mixture are blowing agents or blowing agent blendsas disclosed in this invention. Generally speaking, the amount ofblowing agent present in the blended mixture is dictated by the desiredfoam densities of the final polyurethane or polyisocyanurate foamsproduct. The proportions in parts by weight of the total blowing agentblend can fall within the range of from 1 to about 45 parts of blowingagent per 100 parts of polyol, preferably from about 4 to about 30parts.

The polyurethane foams produced can vary in density from about 0.5 poundper cubic foot to about 40 pounds per cubic foot, preferably from about1.0 to 20.0 pounds per cubic foot, and most preferably from about 1.5 to6.0 pounds per cubic foot. The density obtained is a function of howmuch of the blowing agent or blowing agent mixture disclosed in thisinvention is present in the A and/or B components, or alternativelyadded at the time the foam is prepared.

Foams and Foamable Compositions:

Certain embodiments of the present invention involve a foam comprising apolyurethane-, polyisocyanurate-, or phenolic-based cell wall and a cellgas disposed within at least a portion of the cells, wherein the cellgas comprises the azeotrope-like mixture described herein. In certainembodiments, the foams are extruded thermoplastic foams. Preferred foamshave a density ranging from about 0.5 pounds per cubic foot to about 60pounds per cubic foot, preferably from about 1.0 to 20.0 pounds percubic foot, and most preferably from about 1.5 to 6.0 pounds per cubicfoot. The foam density is a function of how much of the blowing agent orblowing agent mixture (i.e., the azeotrope-like mixture and anyauxiliary blowing agent, such as carbon dioxide, chemical blowing agentor other co-blowing agent) is present in the molten polymer. These foamsare generally rigid but can be made in various grades of softness tosuit the end use requirements. The foams can have a closed cellstructure, an open cell structure or a mixture of open and closed cells,with closed cell structures being preferred. These foams are used in avariety of well known applications, including but not limited to thermalinsulation, flotation, packaging, void filling, crafts and decorative,and shock absorption.

In other embodiments, the invention provides foamable compositions. Thefoamable compositions of the present invention generally include one ormore components capable of forming foam, such as polyurethane,polyisocyanurate, and phenolic-based compositions, and a blowing agentcomprising at least one azeotrope-like mixture described herein. Incertain embodiments, the foamable composition comprises thermoplasticmaterials, particularly thermoplastic polymers and/or resins. Examplesof thermoplastic foam components include polyolefins, such aspolystyrene (PS), polyethylene (PE), polypropylene (PP) andpolyethyleneterepthalate (PET), and foams formed therefrom, preferablylow-density foams. In certain embodiments, the thermoplastic foamablecomposition is an extrudable composition.

In certain embodiments, provided is a method for producing such foams.It will be appreciated by those skilled in the art, especially in viewof the disclosure contained herein, that the order and manner in whichthe blowing agent is formed and/or added to the foamable compositiondoes not generally affect the operability of the present invention. Forexample, in the case of extrudable foams, it is possible to mix inadvance the various components of the blowing agent. In certainembodiments, the components of the foamable composition are not mixed inadvance of introduction to the extrusion equipment or are not added tothe same location in the extrusion equipment. Thus, in certainembodiments it may be desired to introduce one or more components of theblowing agent at first location in the extruder, which is upstream ofthe place of addition of one or more other components of the blowingagent, with the expectation that the components will come together inthe extruder and/or operate more effectively in this manner. In certainother embodiments, two or more components of the blowing agent arecombined in advance and introduced together into the foamablecomposition, either directly or as part of premix which is then furtheradded to other parts of the foamable composition.

Sprayable Compositions:

In a preferred embodiment, the azeotrope-like compositions of thisinvention may be used as solvents in sprayable compositions, eitheralone or in combination with other known propellants. The solventcomposition comprises, more preferably consists essentially of, and,even more preferably, consists of the azeotrope-like compositions of theinvention. In certain embodiments, the sprayable composition is anaerosol.

In certain preferred embodiments, provided is a sprayable compositioncomprising a solvent as described above, an active ingredient, andoptionally, other components such as inert ingredients, solvents, andthe like.

Suitable active materials to be sprayed include, without limitation,cosmetic materials such as deodorants, perfumes, hair sprays, cleaningsolvents, lubricants, insecticides as well as medicinal materials, suchas anti-asthma medications. The term medicinal materials is used hereinin its broadest sense to include any and all materials which are, or atleast are believe to be, effective in connection with therapeutic,diagnostic, pain relief, and similar treatments, and as such wouldinclude for example drugs and biologically active substances.

Solvents and Cleaning Compositions:

In another embodiment of the invention, the azeotrope-like compositionsdescribed herein can be used as a solvent in cleaning various soils suchas mineral oil, rosin based fluxes, silicon oils, lubricants, etc., fromvarious substrates by wiping, vapor degreasing, or other means. Incertain preferred embodiments, the cleaning composition is an aerosol.

EXAMPLES

The invention is further illustrated in the following example which isintended to be illustrative, but not limiting in any manner. For therelevant examples, an ebulliometer of the general type described bySwietolslowski in his book “Ebulliometric Measurements” (Reinhold, 1945)was used.

Example 1

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which was further equipped with a Quartz Thermometer or a thermistorwas used. About 10 cc of trans-HFO-1233zd was charged to theebulliometer and then methanol was added in small, measured increments.Temperature depression was observed when methanol was added, indicatinga binary minimum boiling azeotrope had been formed. From greater than 0to about 51 weight percent methanol, the boiling point of thecomposition changes less than about 1.3° C. The boiling points of thebinary mixtures shown in Table 1 changed by less than about 0.02° C.Thus the compositions exhibited azeotrope and/or azeotrope-likeproperties over these ranges. To conform result two such ebulliometerswere set up side by side of which one contained pure solvent and theother one was set up with trans-HFO-1233zd and 2^(nd) component wasadded as mentioned before. The difference of temperatures in the two wasalso measured.

TABLE 1 trans-HFO-1233zd/Methanol compositions at ambient pressure Wt. %trans- wt % Temp (° C. ) HFO-1233zd Methanol 17.15 (° C.) 98.78 wt. %1.22 wt. % 17.14 (° C.) 98.58 wt. % 1.42 wt. % 17.14 (° C.) 98.38 wt. %1.62 wt. % 17.14 (° C.) 98.18 wt. % 1.82 wt. % 17.14 (° C.) 97.98 wt. %2.02 wt. % 17.14 (° C.) 97.78 wt. % 2.22 wt. % 17.15 (° C.) 97.59 wt. %2.41 wt. %

Example 2

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which was further equipped with a Quartz Thermometer or a thermistorwas used. About 35 g trans-HFO-1233zd is charged to the ebulliometer andthen n-pentane was added in small, measured increments. Temperaturedepression was observed when n-pentane was added to trans-HFO-1233zd,indicating a binary minimum boiling azeotrope had been formed. Fromgreater than 0 to about 30 weight percent n-pentane, the boiling pointof the composition changes less than about 0.8° C. The boiling points ofthe binary mixtures shown in Table 2 changed by less than about 0.02° C.Thus the compositions exhibited azeotrope and/or azeotrope-likeproperties over these ranges.

TABLE 2 trans-HFO-1233zd/n-Pentane compositions at ambient pressure Wt.% trans- Wt % Temp (° C.) HFO-1233zd n-pentane 17.43 (° C.) 97.76 wt. %2.24 wt. % 17.42 (° C.) 97.60 wt. % 2.40 wt. % 17.42 (° C.) 97.45 wt. %2.55 wt. % 17.42 (° C.) 97.29 wt. % 2.71 wt. % 17.42 (° C.) 97.14 wt. %2.86 wt. % 17.42 (° C.) 96.98 wt. % 3.02 wt. % 17.42 (° C.) 96.83 wt. %3.17 wt. % 17.42 (° C.) 96.67 wt. % 3.33 wt. % 17.42 (° C.) 96.52 wt. %3.48 wt. % 17.42 (° C.) 96.37 wt. % 3.63 wt. % 17.42 (° C.) 96.22 wt. %3.78 wt. % 17.42 (° C.) 96.07 wt. % 3.93 wt. % 17.43 (° C.) 95.92 wt. %4.08 wt. %

Example 3

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which was further equipped with a Quartz Thermometer or a thermistorwas used. About 17 g trans-HFO-1233zd is charged to the ebulliometer andthen isopentane was added in small, measured increments. Temperaturedepression was observed when isopentane was added to trans-HFO-1233zd,indicating a binary minimum boiling azeotrope had been formed. Fromgreater than about 0 to about 30 weight percent isopentane, the boilingpoint of the composition changed by about 0.8° C. or less. The boilingpoints of the binary mixtures shown in Table 3 changed by less thanabout 0.2° C. Thus the compositions exhibited azeotrope and/orazeotrope-like properties over these ranges.

TABLE 3 trans-HFO-1233/isopentane compositions at ambient pressure Wt %trans- Wt % Temp(° C. ) HFO-1233zd isopentane 16.86 (° C.) 92.39 wt. % 7.61 wt. % 16.78 (° C.) 90.52 wt. %  9.48 wt. % 16.73 (° C.) 88.73 wt.% 11.27 wt. % 16.70 (° C.) 87.01 wt. % 12.99 wt. % 16.70 (° C.) 85.35wt. % 14.65 wt. % 16.69 (° C.) 83.75 wt. % 16.25 wt. % 16.70 (° C.)82.21 wt. % 17.79 wt. % 16.72 (° C.) 80.73 wt. % 19.27 wt. % 16.76 (°C.) 79.13 wt. % 20.87 wt. % 16.85 (° C.) 77.58 wt. % 22.42 wt. %

Example 4

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which was further equipped with a Quartz Thermometer or a thermistorwas used. About 17 g neopentane is charged to the ebulliometer and thentrans-HFO-1233zd was added in small, measured increments. Temperaturedepression was observed when trans-HFO-1233zd was added to neopentaneindicating a binary minimum boiling azeotrope had been formed. As shownin Table 4, compositions comprising from about 19 to about 49 weightpercent trans-HFO-1233zd had a change in boiling point of 0.1° C. orless. Thus the compositions exhibited azeotrope and/or azeotrope-likeproperties over at least this range.

TABLE 4 trans-HFO-1233zd/neopentane compositions at ambient pressure Wt% trans- Wt % Temp(° C. ) HFO-1233zd neopentane 8.54 (° C.)  0.00 wt. %100.00 wt. %  8.47 (° C.)  1.36 wt. % 98.64 wt. % 8.42 (° C.)  2.69 wt.% 97.31 wt. % 8.30 (° C.)  5.23 wt. % 94.77 wt. % 8.21 (° C.)  7.65 wt.% 92.35 wt. % 8.12 (° C.)  9.94 wt. % 90.06 wt. % 7.95 (° C.) 14.21 wt.% 85.79 wt. % 7.87 (° C.) 19.00 wt. % 81.00 wt. % 7.78 (° C.) 23.29 wt.% 76.71 wt. % 7.72 (° C.) 29.28 wt. % 70.72 wt. % 7.72 (° C.) 34.40 wt.% 65.60 wt. % 7.75 (° C.) 38.83 wt. % 61.17 wt. % 7.81 (° C.) 42.70 wt.% 57.30 wt. % 7.85 (° C.) 46.11 wt. % 53.89 wt. % 7.88 (° C.) 49.14 wt.% 50.86 wt. %

Example 5

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which was further equipped with a Quartz Thermometer or a thermistorwas used. About 18 g trans-HFO-1233 is charged to the ebulliometer andthen trans-1,2-DCE was added in small, measured increments. Temperaturedepression was observed when trans-1,2-DCE was added to trans-HFO-1233,indicating a binary minimum boiling azeotrope was formed. From greaterthan about 0.01 to about 53 weight percent trans-1,2-DCE, the boilingpoint of the composition changed by about 0.7° C. or less. The boilingpoints of the binary mixtures shown in Table 4 changed by less thanabout 0.3° C. Thus the compositions exhibited azeotrope and/orazeotrope-like properties over these ranges.

TABLE 5 trans-HFO-1233zd/trans-1,2-DCE compositions at ambient pressureWt. % trans- Wt. % T(° C.) HFO-1233zd tr-1,2-DCE 17.74 (° C.) 100.00 wt.%  0.00 wt. % 17.74 (° C.) 99.68 wt. % 0.32 wt. % 17.73 (° C.) 99.35 wt.% 0.65 wt. % 17.76 (° C.) 99.03 wt. % 0.97 wt. % 17.79 (° C.) 98.72 wt.% 1.28 wt. % 17.82 (° C.) 98.40 wt. % 1.60 wt. % 17.85 (° C.) 98.08 wt.% 1.92 wt. % 17.88 (° C.) 97.77 wt. % 2.23 wt. % 17.92 (° C.) 97.46 wt.% 2.54 wt. % 17.96 (° C.) 97.15 wt. % 2.85 wt. %

Examples 6-23

The general procedure described in examples 1-5 above was repeated forexamples 6-23. Azeotrope-like behavior was observed over a given rangeof component concentrations where the boiling point changed by ≦1° C.The results are summarized below:

Boiling Relative Concentration Point (° C.) 1233zd: Other @ ambient DataAzeotrope-like mixture Component(s) (wt. %) pressure Tabletrans-HFO-1233zd + isohexane 94.4-99.99/0.01-5.6  17.4 ± 1 6trans-HFO-1233zd + ethanol 85-99.9/0.1-15 18.1 ± 1 7 trans-HFO-1233zd +isopropanol 90-99.9/0.1-10 17.9 ± 1 8 trans-HFO-1233zd + 1-chloropropane96-99.9/0.1-4    18 ± 1 9 trans-HFO-1233zd + 2-chloropropane94-99.99/0.01-6  17.8 ± 1 10 trans-HFO-1233zd + cyclopentene95-99.9/0.1-5  18.1 ± 1 11 trans-HFO-1233zd + cyclopentane95-99.9/0.1-5  17.5 ± 1 12 trans-HFO-1233zd + methylal 95-99.9/0.1-5 17.3 ± 1 13 trans-HFO-1233zd + methyl acetate 90-99.9/0.1-5  17.5 ± 1 14trans-HFO-1233zd + HFC-365mfc 89-99.9/0.1-11 17.5 ± 1 15trans-HFO-1233zd + n-hexane 95-99.99/0.01-5  17.4 ± 1 16cis-HFO-1233zd + methanol 78-99.9/0.1-22 35.2 ± 1 17 cis-HFO-1233zd +ethanol 65-99.9/0.1-35 37.4 ± 1 18 cis-HFO-1233zd + isopropanol85-99.99/0.01-15 38.1 ± 1 19 cis-HFO-1233zd + cyclopentane 42-99/1-5834.7 ± 1 20 cis-HFO-1233zd + trans-1,2-DCE 42-99.9/0.1-58   37 ± 1 21trans-HFO-1233zd + trans-1,2-DCE + 55-99.9/0.05-10/0.05-35 17.4 ± 1 22n-pentane trans-HFO-1233zd + trans-1,2-DCE +   80-09/0.05-15/0.05-1016.6 ± 1 23 methanol

TABLE 6 trans-HFO-1233zd/isohexane compositions at ambient pressureisohexane (wt. %) trans-1233zd (wt. %) Boiling Point (° C.) 0.0 100.017.5 0.2 99.8 17.5 0.3 99.7 17.6 0.5 99.5 17.6 0.7 99.3 17.6 0.8 99.217.6 1.0 99.0 17.7 1.2 98.8 17.7 1.3 98.7 17.7 1.5 98.5 17.8 1.7 98.317.8 1.8 98.2 17.8 2.0 98.0 17.8 2.2 97.8 17.9 2.3 97.7 17.9 2.5 97.517.9 2.6 97.4 18.0 2.8 97.2 18.0 3.0 97.0 18.0 3.1 96.9 18.1 3.3 96.718.1 3.4 96.6 18.1 3.6 96.4 18.2 3.8 96.2 18.2 3.9 96.1 18.2 4.1 95.918.2 4.2 95.8 18.3 4.4 95.6 18.3 4.5 95.5 18.3 4.7 95.3 18.4 4.9 95.118.4 5.0 95.0 18.4 5.2 94.8 18.4

TABLE 7 trans-HFO-1233zd/ethanol compositions at ambient pressure EtOH(wt. %) trans-1233zd (wt. %) Boiling Point (° C.) 0.0 100.0 18.1 0.299.8 18.1 0.4 99.6 18.1 0.6 99.4 18.1 0.8 99.2 18.1 1.0 99.0 18.1 1.298.8 18.1 1.4 98.6 18.1 1.6 98.4 18.1 1.8 98.2 18.2 2.0 98.0 18.2 2.297.8 18.2 2.4 97.6 18.1 2.6 97.4 18.1 2.8 97.2 18.2 3.0 97.0 18.2 3.296.8 18.2 3.4 96.6 18.2 3.6 96.4 18.2 3.8 96.2 18.2 4.0 96.0 18.2 4.195.9 18.2 4.3 95.7 18.2 4.5 95.5 18.2 4.7 95.3 18.2 4.9 95.1 18.2 5.194.9 18.2

TABLE 8 trans-HFO-1233zd/isopropanol compositions at ambient pressureIPA (wt. %) trans-1233zd (wt. %) Boiling Point (° C.) 0.0 100.0 17.9 0.499.6 17.9 0.8 99.2 17.9 1.2 98.8 17.9 1.6 98.4 17.9 2.0 98.0 17.9 2.497.6 17.9 2.8 97.2 18.0 3.2 96.8 18.0 3.5 96.5 18.1 3.9 96.1 18.1 4.395.7 18.1 4.7 95.3 18.2 5.0 95.0 18.2 5.4 94.6 18.2 5.8 94.2 18.3 6.193.9 18.3 6.5 93.5 18.3 6.9 93.1 18.3 7.2 92.8 18.4 7.6 92.4 18.4 7.992.1 18.4 8.3 91.7 18.4 8.6 91.4 18.4 8.9 91.1 18.5 9.3 90.7 18.5 9.690.4 18.5

TABLE 9 trans-HFO-1233zd/1-chloropropane compositions at ambientpressure 1-chloropropane (wt. %) trans-1233zd (wt. %) Boiling Point (°C.) 0.0 100.0 18.0 0.2 99.8 18.0 0.5 99.5 18.0 0.7 99.3 18.0 0.9 99.118.0 1.1 98.9 18.1 1.4 98.6 18.1 1.6 98.4 18.2 1.8 98.2 18.2 2.0 98.018.3 2.3 97.7 18.3 2.5 97.5 18.4 2.7 97.3 18.5 2.9 97.1 18.5 3.1 96.918.6 3.4 96.6 18.6 3.6 96.4 18.6 3.8 96.2 18.7 4.0 96.0 18.8 4.2 95.818.8 4.4 95.6 18.8 4.6 95.4 18.9 4.9 95.1 18.9 5.1 94.9 19.0 5.3 94.719.0 5.5 94.5 19.1 5.7 94.3 19.1

TABLE 10 trans-HFO-1233zd/2-chloropropane compositions at ambientpressure 2-chloropropane (wt. %) trans-1233zd (wt. %) Boiling Point (°C.) 0.0 100.0 17.8 0.2 99.8 17.8 0.4 99.6 17.8 0.7 99.3 17.8 0.9 99.117.8 1.1 98.9 17.9 1.3 98.7 17.9 1.5 98.5 17.9 1.8 98.2 17.9 2.0 98.018.0 2.2 97.8 18.0 2.4 97.6 18.0 2.6 97.4 18.0 2.8 97.2 18.0 3.0 97.018.0 3.3 96.7 18.0 3.5 96.5 18.1 3.7 96.3 18.1 3.9 96.1 18.1 4.1 95.918.1 4.3 95.7 18.1 4.5 95.5 18.1 4.7 95.3 18.2 4.9 95.1 18.2 5.1 94.918.2 5.3 94.7 18.2 5.5 94.5 18.2 5.7 94.3 18.2 5.9 94.1 18.2 6.1 93.918.2 6.3 93.7 18.3

TABLE 11 trans-HFO-1233zd/cyclopentene compositions at ambient pressurecyclopentene (wt. %) trans-1233zd (wt. %) Boiling Point (° C.) 0.0 100.017.8 0.2 99.8 17.8 0.4 99.6 17.8 0.6 99.4 17.9 0.8 99.2 17.9 1.0 99.017.9 1.2 98.8 18.0 1.4 98.6 18.0 1.6 98.4 18.0 1.8 98.2 18.1 2.0 98.018.1 2.2 97.8 18.1 2.4 97.6 18.2 2.5 97.5 18.2 2.7 97.3 18.2 2.9 97.118.3 3.1 96.9 18.3 3.3 96.7 18.3 3.5 96.5 18.3 3.7 96.3 18.4 3.9 96.118.4 4.1 95.9 18.4 4.2 95.8 18.4 4.4 95.6 18.5 4.6 95.4 18.5 4.8 95.218.5

TABLE 12 trans-HFO-1233zd/cyclopentane compositions at ambient pressurecyclopentane (wt. %) trans-1233zd (wt. %) Boiling Point (° C.) 0.0 100.017.6 0.2 99.8 17.6 0.4 99.6 17.7 0.6 99.4 17.7 1.0 99.0 17.8 1.3 98.717.8 1.7 98.3 17.8 2.1 97.9 17.8 2.5 97.5 17.9 2.8 97.2 17.9 3.2 96.818.0 3.6 96.4 18.1 3.9 96.1 18.1 4.3 95.7 18.2 4.6 95.4 18.2 5.0 95.018.3 5.3 94.7 18.3 5.7 94.3 18.4

TABLE 13 trans-HFO-1233zd/methylal compositions at ambient pressuremethylal (wt. %) trans-1233zd (wt. %) Boiling Point (° C.) 0.0 100.017.5 0.2 99.8 17.5 0.4 99.6 17.5 0.7 99.3 17.3 0.9 99.1 17.4 1.1 98.917.4 1.3 98.7 17.5 1.5 98.5 17.6 1.8 98.2 17.7 2.0 98.0 17.8 2.2 97.817.9 2.4 97.6 18.0 2.6 97.4 18.1 2.8 97.2 18.2 3.1 96.9 18.2 3.3 96.718.3 3.5 96.5 18.4 3.7 96.3 18.5 3.9 96.1 18.6 4.1 95.9 18.6 4.3 95.718.7 4.5 95.5 18.8 4.7 95.3 18.8 4.9 95.1 18.9 5.1 94.9 18.9

TABLE 14 trans-HFO-1233zd/methyl acetate compositions at ambientpressure Me-Acetate (wt. %) trans-1233zd (wt. %) Boiling Point (° C.)0.0 100.0 17.6 0.2 99.8 17.7 0.4 99.6 17.7 0.7 99.3 17.8 0.9 99.1 17.91.1 98.9 18.0 1.3 98.7 18.0 1.5 98.5 18.1 1.8 98.2 18.2 2.0 98.0 18.32.2 97.8 18.3 2.4 97.6 18.4 2.6 97.4 18.4 2.8 97.2 18.5 3.1 96.9 18.63.3 96.7 18.6 3.5 96.5 18.7 3.7 96.3 18.7

TABLE 15 trans-HFO-1233zd/HFC-365mfc compositions at ambient pressureHFC-365mfc (wt. %) trans-1233zd (wt. %) Boiling Point (° C.) 0.0 100.017.6 0.3 99.7 17.6 0.6 99.4 17.6 1.0 99.0 17.6 1.3 98.7 17.7 1.6 98.417.7 1.9 98.1 17.7 2.2 97.8 17.7 2.5 97.5 17.8 2.9 97.1 17.8 3.2 96.817.8 3.5 96.5 17.8 3.8 96.2 17.9 4.1 95.9 17.9 4.4 95.6 17.9 4.7 95.317.9 5.0 95.0 18.0 5.3 94.7 18.0 5.5 94.5 18.0 5.8 94.2 18.0 6.1 93.918.1 6.4 93.6 18.1 6.7 93.3 18.1 7.0 93.0 18.1 7.3 92.7 18.1 7.5 92.518.2 7.8 92.2 18.2 8.1 91.9 18.2 8.4 91.6 18.2

TABLE 16 trans-HFO-1233zd/n-hexane compositions at ambient pressuren-hexane (wt. %) trans-1233zd (wt. %) Boiling Point (° C.) 0.0 100.017.3 0.2 99.8 17.3 0.3 99.7 17.4 0.5 99.5 17.4 0.7 99.3 17.4 0.9 99.117.5 1.0 99.0 17.5 1.2 98.8 17.5 1.4 98.6 17.6 1.5 98.5 17.6 1.7 98.317.6 1.9 98.1 17.7 2.0 98.0 17.7

TABLE 17 cis-HFO-1233zd/methanol compositions at ambient pressuremethanol (wt. %) cis-1233zd (wt. %) Boiling Point (° C.) 0.0 100.0 37.50.6 99.4 36.6 1.2 98.8 35.8 1.8 98.2 35.5 2.4 97.6 35.3 3.0 97.0 35.23.6 96.4 35.2 4.2 95.8 35.2 4.7 95.3 35.2 5.3 94.7 35.2 5.9 94.1 35.36.9 93.1 35.4 8.0 92.0 35.4 9.1 90.9 35.5 10.1 89.9 35.5 11.1 88.9 35.612.0 88.0 35.6 13.0 87.0 35.6 13.9 86.1 35.7 14.8 85.2 35.7 15.7 84.335.8 16.6 83.4 35.8 17.5 82.5 35.9 18.3 81.7 35.9 19.1 80.9 36.0 19.980.1 36.0 20.7 79.3 36.1 21.5 78.5 36.1 22.2 77.8 36.2 23.0 77.0 36.223.7 76.3 36.3 24.4 75.6 36.3 25.1 74.9 36.3 25.8 74.2 36.4 26.5 73.536.4 27.2 72.8 36.5 27.8 72.2 36.5

TABLE 18 cis-HFO-1233zd/ethanol compositions at ambient pressure ethanol(wt. %) cis-1233zd (wt. %) Boiling Point (° C.) 0.0 100.0 37.8 0.6 99.437.7 1.2 98.8 37.6 1.8 98.2 37.6 2.4 97.6 37.6 3.0 97.0 37.6 3.6 96.437.5 4.2 95.8 37.4 4.7 95.3 37.4 5.9 94.1 37.5 6.9 93.1 37.5 8.0 92.037.4 9.1 90.9 37.5 10.1 89.9 37.5 11.1 88.9 37.6 12.0 88.0 37.5 13.087.0 37.6 13.9 86.1 37.5 14.8 85.2 37.6 15.7 84.3 37.7 16.6 83.4 37.717.5 82.5 37.7 18.3 81.7 37.7 19.1 80.9 37.7 19.9 80.1 37.6 20.7 79.337.6 21.5 78.5 37.7 22.2 77.8 37.7 23.0 77.0 37.8 23.7 76.3 37.8 24.475.6 37.8 25.1 74.9 37.8 25.8 74.2 37.8 26.5 73.5 37.8 27.2 72.8 37.827.8 72.2 37.9 28.5 71.5 37.9 29.1 70.9 37.9

TABLE 19 cis-HFO-1233zd/isopropanol compositions at ambient pressure IPA(wt. %) cis-1233zd (wt. %) Boiling Point (° C.) 0.0 100.0 38.1 0.6 99.438.1 1.2 98.8 38.1 1.8 98.2 38.2 3.0 97.0 38.2 4.1 95.9 38.3 5.3 94.738.4 6.4 93.6 38.5 7.4 92.6 38.6 8.5 91.5 38.6 9.5 90.5 38.7 10.5 89.538.7 11.5 88.5 38.8 12.4 87.6 38.8 13.4 86.6 38.8

TABLE 20 cis-HFO-1233zd/cyclopentane compositions at ambient pressurecyclopentane (wt. %) cis-1233zd (wt. %) Boiling Point (° C.) 0.0 100.037.5 1.2 98.8 37.1 2.3 97.7 36.6 3.4 96.6 36.3 4.5 95.5 36.0 5.6 94.435.8 6.6 93.4 35.6 7.6 92.4 35.5 8.6 91.4 35.3 9.6 90.4 35.3 10.6 89.435.2 11.5 88.5 35.1 12.4 87.6 35.0 13.3 86.7 35.0 14.2 85.8 35.0 15.184.9 35.0 15.9 84.1 34.9 16.7 83.3 34.9 17.6 82.4 34.9 18.3 81.7 34.919.1 80.9 34.9 19.9 80.1 34.9 20.6 79.4 34.9 21.4 78.6 34.9 22.1 77.934.8 22.8 77.2 34.8 23.5 76.5 34.7 24.2 75.8 34.7 24.9 75.1 34.7 25.574.5 34.7 26.2 73.8 34.7 26.8 73.2 34.8 27.5 72.5 34.8 28.1 71.9 34.828.7 71.3 34.8 29.3 70.7 34.8 29.9 70.1 34.8

TABLE 21 cis-HFO-1233zd/trans-1,2-DCE compositions at ambient pressuretrans-1,2-DCE (wt. %) cis-1233zd (wt. %) Boiling Point (° C.) 0.0 100.037.8 1.0 99.0 37.8 1.9 98.1 37.8 3.8 96.2 37.7 7.3 92.7 37.5 10.6 89.437.4 13.7 86.3 37.2 16.5 83.5 37.1 19.2 80.8 37.1 21.7 78.3 37.0 24.175.9 37.0 26.3 73.7 37.0 28.4 71.6 37.1 30.3 69.7 37.1 32.2 67.8 37.134.0 66.0 37.1 35.7 64.3 37.1 37.3 62.7 37.1 38.8 61.2 37.1 40.2 59.837.1 41.6 58.4 37.2 42.9 57.1 37.2 44.2 55.8 37.2 45.4 54.6 37.3 46.653.4 37.3 47.7 52.3 37.3 48.2 51.8 37.4 48.7 51.3 37.4 49.2 50.8 37.449.7 50.3 37.4 50.2 49.8 37.4 50.7 49.3 37.5 51.2 48.8 37.5 51.7 48.337.5 52.1 47.9 37.5 52.6 47.4 37.6 53.0 47.0 37.6 53.4 46.6 37.6 53.946.1 37.6 54.3 45.7 37.6 54.7 45.3 37.6 55.1 44.9 37.6

TABLE 22 trans-HFO-1233zd/methanol/n-pentane compositions at ambientpressure n-pentane trans-1233zd methanol Boiling Point (wt. %) (wt. %)(wt. %) (° C.) 0.0 98.0 2.0 17.1 0.2 97.8 2.0 17.1 0.3 97.7 2.0 17.1 0.597.5 2.0 17.1 0.6 97.4 2.0 17.1 0.8 97.2 2.0 17.1 1.0 97.1 2.0 17.1 1.196.9 2.0 17.1 1.3 96.7 2.0 17.1 1.4 96.6 2.0 17.1 1.6 96.4 2.0 17.1 1.796.3 2.0 17.1 1.9 96.1 2.0 17.0 2.0 96.0 2.0 17.0 2.2 95.9 2.0 17.0 2.395.7 2.0 17.0 2.5 95.6 2.0 17.0 2.6 95.4 1.9 17.0 2.8 95.3 1.9 17.0 2.995.1 1.9 17.0 3.1 95.0 1.9 17.0 3.2 94.8 1.9 17.0 3.4 94.7 1.9 17.0 3.594.6 1.9 17.0 3.6 94.4 1.9 17.0 3.8 94.3 1.9 17.0 3.9 94.2 1.9 17.0 4.194.0 1.9 17.0 4.2 93.9 1.9 17.0 4.3 93.7 1.9 17.0 4.5 93.6 1.9 17.0 4.693.5 1.9 17.0 4.7 93.4 1.9 17.0 4.9 93.2 1.9 17.0 5.0 93.1 1.9 17.0 5.193.0 1.9 17.0 5.3 92.8 1.9 17.0 5.4 92.7 1.9 17.0 5.5 92.6 1.9 17.0 5.792.4 1.9 17.0 5.8 92.3 1.9 17.0 5.9 92.2 1.9 17.0 6.0 92.1 1.9 17.0 6.291.9 1.9 17.1 6.3 91.8 1.9 17.1 6.4 91.7 1.9 17.1 6.5 91.6 1.9 17.1 6.791.5 1.9 17.1 6.8 91.3 1.9 17.1 6.9 91.2 1.9 17.1 7.0 91.1 1.9 17.1 7.291.0 1.9 17.1 7.3 90.9 1.9 17.1 7.4 90.8 1.9 17.1 7.5 90.6 1.8 17.1 7.690.5 1.8 17.1 7.8 90.4 1.8 17.1 7.9 90.3 1.8 17.1 8.0 90.2 1.8 17.1 8.190.1 1.8 17.1 8.2 90.0 1.8 17.1 8.3 89.8 1.8 17.1 8.4 89.7 1.8 17.1 8.689.6 1.8 17.1 8.7 89.5 1.8 17.1 8.8 89.4 1.8 17.1 8.9 89.3 1.8 17.1 9.089.2 1.8 17.1 9.1 89.1 1.8 17.1 9.2 89.0 1.8 17.1 9.3 88.9 1.8 17.1 9.488.8 1.8 17.1 9.5 88.6 1.8 17.1 9.6 88.5 1.8 17.1 9.8 88.4 1.8 17.2 9.988.3 1.8 17.2 10.1 88.1 1.8 17.2 10.3 87.9 1.8 17.2 10.5 87.7 1.8 17.210.7 87.5 1.8 17.2 10.9 87.3 1.8 17.2 11.1 87.1 1.8 17.2 11.3 86.9 1.817.2 11.5 86.7 1.8 17.2 11.7 86.6 1.8 17.2 11.9 86.4 1.8 17.2 12.1 86.21.8 17.3 12.2 86.0 1.8 17.3 12.4 85.8 1.8 17.3 12.6 85.6 1.7 17.3 12.885.5 1.7 17.3 13.0 85.3 1.7 17.3 13.2 85.1 1.7 17.3 13.3 84.9 1.7 17.313.5 84.8 1.7 17.4 13.7 84.6 1.7 17.4 13.9 84.4 1.7 17.4 14.0 84.3 1.717.4 14.2 84.1 1.7 17.4 14.4 83.9 1.7 17.4 14.5 83.8 1.7 17.4 14.7 83.61.7 17.4 14.9 83.4 1.7 17.5 15.0 83.3 1.7 17.5 15.2 83.1 1.7 17.5 15.383.0 1.7 17.5 15.5 82.8 1.7 17.5 15.6 82.7 1.7 17.5

TABLE 23 trans-HFO-1233zd/methanol/trans-1,2-DCE compositions at ambientpressure trans-1,2-DCE trans-1233zd/methanol Boiling Point (wt. %) (in98:2 wt. ratio) (wt. %) (° C.) 0.0 100.0 16.7 0.3 99.7 16.7 0.6 99.416.8 1.0 99.0 16.8 1.3 98.7 16.8 1.6 98.4 16.9 1.9 98.1 16.9 2.2 97.817.0 2.5 97.5 17.0 2.9 97.1 17.1 3.2 96.8 17.1 3.5 96.5 17.1 3.8 96.217.2 4.1 95.9 17.2 4.4 95.6 17.3 4.7 95.3 17.3 5.0 95.0 17.4 5.3 94.717.4 5.5 94.5 17.4 5.8 94.2 17.5 6.1 93.9 17.5 6.4 93.6 17.6 6.7 93.317.6

Example 24

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which was further equipped with a Quartz Thermometer was used. About10 cc of trans-HFO-1233zd was charged to the ebulliometer and thennitromethane was added in small, measured increments. Temperaturedepression was observed when nitromethane was added, indicating a binaryazeotrope-like composition had been formed.

Wt. % trans- Wt. % Temp (° C.) 1233zd Nitromethane 17.6 100.0 0.0 17.799.7 0.3 17.8 99.4 0.6 17.9 99.1 0.9 18.0 98.8 1.2

Example 25

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which was further equipped with a Quartz Thermometer was used. About10 cc of trans-HFO-1233zd was charged to the ebulliometer and then waterwas added in small, measured increments. Temperature depression wasobserved when water was added, indicating a binary minimum boilingazeotrope had been formed. From greater than 0 to about 30 weightpercent water, the boiling point of the composition changes less thanabout 0.5° C. at ambient pressure.

Temp (° C.) Wt. % trans-1233zd Wt. % Water 17.9 100 0 17.7 99.7 1.4 17.598.6 2.6 17.5 95.8 5.3 17.4 93.2 7.9 17.4 90.7 10.3 17.4 87.5 13.6 17.484.4 16.5 17.4 81.6 19.3 17.4 79.0 21.9 17.4 76.5 24.4 17.4 74.2 26.717.4 72.0 28.8 17.4 69.9 30.9

Example 26

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. Anamount of cis-HFO-1233zd is charged to the ebulliometer and thennitromethane is added in small, measured increments. Temperaturedepression is observed when nitromethane is added to cis-HFO-1233,indicating a binary minimum boiling azeotrope is formed. Thecompositions exhibit azeotrope and/or azeotrope-like properties over arange of about 95 to 99.9 weight percent cis-1233zd and about 0.1 toabout 5 weight percent nitromethane. More pronounced azeotrope and/orazeotrope-like properties occur over a range of about 97 to 99.9 weightpercent cis-1233zd and about 0.1 to about 3 weight percent nitromethane;and even more pronounced over a range of about 99 to 99.9 weight percentcis-1233zd and about 0.1 to about 1 weight percent nitromethane.

Example 27

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. Anamount of cis-HFO-1233zd is charged to the ebulliometer and thenn-pentane is added in small, measured increments. Temperature depressionis observed when n-pentane is added to cis-HFO-1233, indicating a binaryminimum boiling azeotrope is formed. The compositions exhibit azeotropeand/or azeotrope-like properties over a range of about 20 to 99.5 weightpercent cis-1233zd and about 0.5 to about 80 weight percent n-pentane.More pronounced azeotrope and/or azeotrope-like properties occur over arange of about 50 to 99.5 weight percent cis-1233zd and about 0.5 toabout 50 weight percent n-pentane; and even more pronounced over a rangeof about 60 to 99.5 weight percent cis-1233zd and about 0.5 to about 40weight percent n-pentane.

Example 28

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. Anamount of cis-HFO-1233zd is charged to the ebulliometer and thenneopentane is added in small, measured increments. Temperaturedepression is observed when neopentane is added to cis-HFO-1233,indicating a binary minimum boiling azeotrope is formed. Thecompositions exhibit azeotrope and/or azeotrope-like properties over arange of about 5 to 50 weight percent cis-1233zd and about 50 to about95 weight percent neopentane. More pronounced azeotrope and/orazeotrope-like properties occur over a range of about 20 to 45 weightpercent cis-1233zd and about 55 to about 80 weight percent neopentane;and even more pronounced over a range of about 30 to 40 weight percentcis-1233zd and about 60 to about 70 weight percent neopentane.

Example 29

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. Anamount of cis-HFO-1233zd is charged to the ebulliometer and thenn-hexane is added in small, measured increments. Temperature depressionis observed when n-hexane is added to cis-HFO-1233, indicating a binaryminimum boiling azeotrope is formed. The compositions exhibit azeotropeand/or azeotrope-like properties over a range of about 80 to 99.5 weightpercent cis-1233zd and about 0.5 to about 20 weight percent n-hexane.More pronounced azeotrope and/or azeotrope-like properties occur over arange of about 90 to 99.5 weight percent cis-1233zd and about 0.5 toabout 10 weight percent n-hexane; and even more pronounced over a rangeof about 95 to 99.5 weight percent cis-1233zd and about 0.5 to about 5weight percent n-hexane.

Example 30

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. Anamount of cis-HFO-1233zd is charged to the ebulliometer and thenisohexane is added in small, measured increments. Temperature depressionis observed when isohexane is added to cis-HFO-1233, indicating a binaryminimum boiling azeotrope is formed. The compositions exhibit azeotropeand/or azeotrope-like properties over a range of about 70 to 99.5 weightpercent cis-1233zd and about 0.5 to about 30 weight percent isohexane.More pronounced azeotrope and/or azeotrope-like properties occur over arange of about 85 to 99.5 weight percent cis-1233zd and about 0.5 toabout 15 weight percent isohexane; and even more pronounced over a rangeof about 93 to 99.5 weight percent cis-1233zd and about 0.5 to about 7weight percent isohexane.

Example 31

An azeotrope-like mixture containing 98% by weight trans-HFO-1233zd withabout 2% by weight methanol is loaded into an aerosol can. An aerosolvalve is crimped into place and HFC-134a is added through the valve toachieve a pressure in the can of about 20 PSIG. The mixture is thensprayed onto surface demonstrating that the azeotropic mixture is usefulas an aerosol.

Examples 32-57

The steps of Example 31 are generally repeated for Examples 32-57,except that the azeotrope-like mixture identified in the Table below isused instead of trans-HFO-1233zd and methanol. Optionally, the aerosolshave a different co-aerosol agent or no co-aerosol agent, and optionallyhave at least one active ingredient selected from the group consistingof deodorants, perfumes, hair sprays, cleaning solvents, lubricants,insecticides, and medicinal materials. Similar results are demonstrated.

Example Forms No. Azeotrope-like Composition Aerosol 32 trans-1233zd +trans-1,2-DCE Yes 33 trans-1233zd + n-pentane Yes 34 trans-1233zd +isohexane Yes 35 trans-1233zd + neopentane Yes 36 trans-1233zd +methanol/n-pentane Yes 37 trans-1233zd + methanol/trans-1,2-DCE Yes 38trans-1233zd + ethanol Yes 39 trans-1233zd + isopropanol Yes 40trans-1233zd + 1-chloropropane Yes 41 trans-1233zd + 2-chloropropane Yes42 trans-1233zd + cyclopentane Yes 43 trans-1233zd + cyclopentene Yes 44trans-1233zd + methylal Yes 45 trans-1233zd + methyl acetate Yes 46trans-1233zd + n-hexane Yes 47 trans-1233zd + nitromethane Yes 48cis-1233zd + methanol Yes 49 cis-1233zd + ethanol Yes 50 cis-1233zd +isopropanol Yes 51 cis-1233zd + n-hexane Yes 52 cis-1233zd + isohexaneYes 53 cis-1233zd + cyclopentane Yes 54 cis-1233zd + n-pentane Yes 55cis-1233zd + nitromethane Yes 56 cis-1233zd + trans-1,2-DCE Yes 57cis-1233zd + neopentane Yes

Example 58

A mixture containing 98% by weight trans-HFO-1233zd with about 2% byweight methanol is loaded into an aerosol can. An aerosol valve iscrimped into place and HFC-134a is added through the valve to achieve apressure in the can of about 20 PSIG. The mixture is then sprayed onto ametal coupon soiled with solder flux. The flux is removed and the couponis visually clean.

Examples 59-84

For Examples 59-84, the steps of Example 58 are generally repeated,except that the azeotrope-like mixture identified in the Table below isused instead of trans-HFO-1233zd and methanol, and instead of HFC-134a,a different co-aerosol or no co-aerosol is used. Optionally, the methodof applying the azeotropic mixture as a cleaning agent is vapordegreasing or wiping instead of spraying. Optionally, the azeotropicmixture cleaning agent is applied neat. Optionally, the material to becleaned was changed from solder flux to a mineral oil, silicon oil, orother lubricant. Similar results are demonstrated in each case.

Example Visually No. Azeotrope-like Composition Clean 59 trans-1233zd +trans-1,2-DCE Yes 60 trans-1233zd + n-pentane Yes 61 trans-1233zd +isohexane Yes 62 trans-1233zd + neopentane Yes 63 trans-1233zd +methanol/n-pentane Yes 64 trans-1233zd + methanol/trans-1,2-DCE Yes 65trans-1233zd + ethanol Yes 66 trans-1233zd + isopropanol Yes 67trans-1233zd + 1-chloropropane Yes 68 trans-1233zd + 2-chloropropane Yes69 trans-1233zd + cyclopentane Yes 70 trans-1233zd + cyclopentene Yes 71trans-1233zd + methylal Yes 72 trans-1233zd + methyl acetate Yes 73trans-1233zd + n-hexane Yes 74 trans-1233zd + nitromethane Yes 75cis-1233zd + methanol Yes 76 cis-1233zd + ethanol Yes 77 cis-1233zd +isopropanol Yes 78 cis-1233zd + n-hexane Yes 79 cis-1233zd + isohexaneYes 80 cis-1233zd + cyclopentane Yes 81 cis-1233zd + n-pentane Yes 82cis-1233zd + nitromethane Yes 83 cis-1233zd + trans-1,2-DCE Yes 84cis-1233zd + neopentane Yes

Example 85

A mixture containing 98% by wt trans-HFO-1233zd and 2% by wt of methanolis prepared, silicone oil is mixed with the blend and the solvent wasleft to evaporate, a thin coating of silicone oil is left behind in thecoupon. This indicated that the solvent blends can be used for siliconeoil deposition in various substrates.

Examples 86-111

The steps of Example 85 are generally repeated for Examples 85-111,except that the azeotrope-like mixture identified in the Table below isused instead of trans-HFO-1233zd and methanol.

Example Oil No. Azeotrope-like Composition Deposited 86 trans-1233zd +trans-1,2-DCE Yes 87 trans-1233zd + n-pentane Yes 88 trans-1233zd +isohexane Yes 89 trans-1233zd + neopentane Yes 90 trans-1233zd +methanol/n-pentane Yes 91 trans-1233zd + methanol/trans-1,2-DCE Yes 92trans-1233zd + ethanol Yes 93 trans-1233zd + isopropanol Yes 94trans-1233zd + 1-chloropropane Yes 95 trans-1233zd + 2-chloropropane Yes96 trans-1233zd + cyclopentane Yes 97 trans-1233zd + cyclopentene Yes 98trans-1233zd + methylal Yes 99 trans-1233zd + methyl acetate Yes 100trans-1233zd + n-hexane Yes 101 trans-1233zd + nitromethane Yes 102cis-1233zd + methanol Yes 103 cis-1233zd + ethanol Yes 104 cis-1233zd +isopropanol Yes 105 cis-1233zd + n-hexane Yes 106 cis-1233zd + isohexaneYes 107 cis-1233zd + cyclopentane Yes 108 cis-1233zd + n-pentane Yes 109cis-1233zd + nitromethane Yes 110 cis-1233zd + trans-1,2-DCE Yes 111cis-1233zd + neopentane Yes

Example 112

A mixture containing 98% by wt trans-HFO-1233zd and 2% by wt of methanolis prepared, mineral oil is mixed with the blend. The mineral oil isevenly disbursed throughout the blend. This indicated that theazeotrope-like composition can be used as a solvent.

Examples 113-138

The steps of Example 112 are generally repeated for Examples 113-138,except that the azeotrope-like mixture identified in the Table below isused instead of trans-HFO-1233zd and methanol.

Example Good No. Azeotrope-like Composition Solvency 113 trans-1233zd +trans-1,2-DCE Yes 114 trans-1233zd + n-pentane Yes 115 trans-1233zd +isohexane Yes 116 trans-1233zd + neopentane Yes 117 trans-1233zd +methanol/n-pentane Yes 118 trans-1233zd + methanol/trans-1,2-DCE Yes 119trans-1233zd + ethanol Yes 120 trans-1233zd + isopropanol Yes 121trans-1233zd + 1-chloropropane Yes 122 trans-1233zd + 2-chloropropaneYes 123 trans-1233zd + cyclopentane Yes 124 trans-1233zd + cyclopenteneYes 125 trans-1233zd + methylal Yes 126 trans-1233zd + methyl acetateYes 127 trans-1233zd + n-hexane Yes 128 trans-1233zd + nitromethane Yes129 cis-1233zd + methanol Yes 130 cis-1233zd + ethanol Yes 131cis-1233zd + isopropanol Yes 132 cis-1233zd + n-hexane Yes 133cis-1233zd + isohexane Yes 134 cis-1233zd + cyclopentane Yes 135cis-1233zd + n-pentane Yes 136 cis-1233zd + nitromethane Yes 137cis-1233zd + trans-1,2-DCE Yes 138 cis-1233zd + neopentane Yes

Example 139

An azeotrope-like mixture of about 97 weight percent trans-1233zd andabout 3 weight percent trans-1,2-DCE is prepared. This mixture is usedas a blowing agent to prepare a closed-cell polyurethane foam and aclosed-cell polyisocyanate foam. The cell-gas of the resulting foam isanalyzed and is determined to contain at least a portion of theazeotrope-like mixture.

Examples 140-153

The steps of Example 139 are generally repeated for Examples 140-153,except that the azeotrope-like mixture identified in the Table below isused instead of trans-HFO-1233zd and trans-1,2-DCE.

Cell-gas of foam Use as a Polyurethane contains Blowing Foam andAzeotrope- Example Agent Polyisocyanate like No. Azeotrope-likeComposition Verified Foam Formed Mixture 140 trans-1233zd + n-pentaneYes Yes Yes 141 trans-1233zd + isopentane Yes Yes Yes 142 trans-1233zd +neopentane Yes Yes Yes 143 trans-1233zd + 1-chloropropane Yes Yes Yes144 trans-1233zd + 2-chloropropane Yes Yes Yes 145 trans-1233zd +cyclopentane Yes Yes Yes 146 trans-1233zd + cyclopentene Yes Yes Yes 147trans-1233zd + methylal Yes Yes Yes 148 trans-1233zd + methyl acetateYes Yes Yes 149 trans-1233zd + water Yes Yes Yes 150 trans-1233zd +nitromethane Yes Yes Yes 151 cis-1233zd + cyclopentane Yes Yes Yes 152cis-1233zd + n-pentane Yes Yes Yes 153 cis-1233zd + neopentane Yes YesYes

Example 154

Mixtures were prepared containing 98% by weight trans-HFO-1233zd withabout 2 weight percent methanol. Several stainless steel coupons weresoiled with mineral oil. Then these coupons were immersed in thesesolvent blends. The blends removed the oils in a short period of time.The coupons were observed visually and looked clean.

Examples 155-180

The steps of Example 154 are generally repeated for Examples 155-180,except that the azeotrope-like mixture identified in the Table below isused instead of trans-HFO-1233zd and methanol.

Example Visually No. Azeotrope-like Composition Clean 155 trans-1233zd +trans-1,2-DCE Yes 156 trans-1233zd + n-pentane Yes 157 trans-1233zd +isohexane Yes 158 trans-1233zd + neopentane Yes 159 trans-1233zd +methanol/n-pentane Yes 160 trans-1233zd + methanol/trans-1,2-DCE Yes 161trans-1233zd + ethanol Yes 162 trans-1233zd + isopropanol Yes 163trans-1233zd + 1-chloropropane Yes 164 trans-1233zd + 2-chloropropaneYes 165 trans-1233zd + cyclopentane Yes 166 trans-1233zd + cyclopenteneYes 167 trans-1233zd + methylal Yes 168 trans-1233zd + methyl acetateYes 169 trans-1233zd + n-hexane Yes 170 trans-1233zd + nitromethane Yes171 cis-1233zd + methanol Yes 172 cis-1233zd + ethanol Yes 173cis-1233zd + isopropanol Yes 174 cis-1233zd + n-hexane Yes 175cis-1233zd + isohexane Yes 176 cis-1233zd + cyclopentane Yes 177cis-1233zd + n-pentane Yes 178 cis-1233zd + nitromethane Yes 179cis-1233zd + trans-1,2-DCE Yes 180 cis-1233zd + neopentane Yes

Example 181

A solvent blend was prepared containing 98% by wt of trans-HFO-1233zdand 2% by wt of methanol. Kester 1544 Rosin Soldering Flux was placed onstainless steel coupons and heated to approximately 300-400° F., whichsimulates contact with a wave soldier normally used to solder electroniccomponents in the manufacture of printed circuit boards. The couponswere then dipped in the solvent mixture and removed after 15 secondswithout rinsing. Results show that the coupons appeared clean by visualinspection.

Examples 182-207

The steps of Example 181 are generally repeated for Examples 185-207,except that the azeotrope-like mixture identified in the Table below isused instead of trans-HFO-1233zd and methanol.

Example Visually No. Azeotrope-like Composition Clean 182 trans-1233zd +trans-1,2-DCE Yes 183 trans-1233zd + n-pentane Yes 184 trans-1233zd +isohexane Yes 185 trans-1233zd + neopentane Yes 186 trans-1233zd +methanol/n-pentane Yes 187 trans-1233zd + methanol/trans-1,2-DCE Yes 188trans-1233zd + ethanol Yes 189 trans-1233zd + isopropanol Yes 190trans-1233zd + 1-chloropropane Yes 191 trans-1233zd + 2-chloropropaneYes 192 trans-1233zd + cyclopentane Yes 193 trans-1233zd + cyclopenteneYes 194 trans-1233zd + methylal Yes 195 trans-1233zd + methyl acetateYes 196 trans-1233zd + n-hexane Yes 197 trans-1233zd + nitromethane Yes198 cis-1233zd + methanol Yes 199 cis-1233zd + ethanol Yes 200cis-1233zd + isopropanol Yes 201 cis-1233zd + n-hexane Yes 202cis-1233zd + isohexane Yes 203 cis-1233zd + cyclopentane Yes 204cis-1233zd + n-pentane Yes 205 cis-1233zd + nitromethane Yes 206cis-1233zd + trans-1,2-DCE Yes 207 cis-1233zd + neopentane Yes

Having thus described a few particular embodiments of the invention,various alterations, modifications, and improvements will readily occurto those skilled in the art. Such alterations, modifications, andimprovements, as are made obvious by this disclosure, are intended to bepart of this description though not expressly stated herein, and areintended to be within the spirit and scope of the invention.Accordingly, the foregoing description is by way of example only, andnot limiting. The invention is limited only as defined in the followingclaims and equivalents thereto.

1. A composition comprising a binary azeotrope-like mixture consistingessentially of 1-chloro-3,3,3-trifluoropropene and a C₁-C₃ alcoholselected from the group consisting of methanol, ethanol, andisopropanol.
 2. The composition of claim 1 wherein said azeotrope-likemixture consists essentially of about 78 to about 99.9 weight percentcis-1-chloro-3,3,3-trifluoropropene and about 0.1 to about 22 weightpercent methanol.
 3. The composition of claim 1 wherein saidazeotrope-like mixture consists essentially of about 85 to about 99.9weight percent trans-1-chloro-3,3,3-trifluoropropene and about 0.1 toabout 15 weight percent ethanol.
 4. The composition of claim 1 whereinsaid azeotrope-like mixture consists essentially of about 65 to about99.9 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.1 toabout 35 weight percent ethanol.
 5. The composition of claim 1 whereinsaid azeotrope-like mixture consists essentially of about 90 to about99.9 weight percent trans-1-chloro-3,3,3-trifluoropropene and about 0.1to about 10 weight percent isopropanol.
 6. The composition of claim 1wherein said azeotrope-like mixture consists essentially of about 85 toabout 99.9 weight percent cis-1-chloro-3,3,3-trifluoropropene and about0.1 to about 15 weight percent isopropanol.
 7. A composition comprisinga binary azeotrope-like mixture consisting essentially of1-chloro-3,3,3-trifluoropropene and a C₅-C₆ hydrocarbon selected fromthe group consisting of n-pentane, isopentane, n-hexane, isohexane,neopentane, cyclopentane, and cyclopentene.
 8. The composition of claim7 wherein said azeotrope-like mixture consists essentially of about 20to about 99.5 weight percent cis-1-chloro-3,3,3-trifluoropropene andabout 0.5 to about 80 weight percent n-pentane.
 9. The composition ofclaim 7 wherein said azeotrope-like mixture consists essentially ofabout 5 to about 50 weight percent cis-1-chloro-3,3,3-trifluoropropeneand about 0.1 to about 40 weight percent neopentane.
 10. The compositionof claim 7 wherein said azeotrope-like mixture consists essentially ofabout 95 to about 99.9 weight percenttrans-1-chloro-3,3,3-trifluoropropene and about 0.1 to about 5 weightpercent cyclopentane.
 11. The composition of claim 7 wherein saidazeotrope-like mixture consists essentially of about 42 to about 99weight percent cis-1-chloro-3,3,3-trifluoropropene and about 1 to about58 weight percent cyclopentane.
 12. The composition of claim 7 whereinsaid azeotrope-like mixture consists essentially of about 95 to about99.9 weight percent trans-1-chloro-3,3,3-trifluoropropene and about 0.1to about 5 weight percent cyclopentene.
 13. The composition of claim 7wherein said azeotrope-like mixture consists essentially of about 95 toabout 99.99 weight percent trans-1-chloro-3,3,3-trifluoropropene andabout 0.01 to about 5 weight percent n-hexane.
 14. The composition ofclaim 7 wherein said azeotrope-like mixture consists essentially ofabout 80 to about 99.5 weight percentcis-1-chloro-3,3,3-trifluoropropene and about 0.5 to about 20 weightpercent n-hexane.
 15. The composition of claim 7 wherein saidazeotrope-like mixture consists essentially of about 94.4 to about 99.99weight percent trans-1-chloro-3,3,3-trifluoropropene and about 0.01 toabout 5.6 weight percent isohexane.
 16. The composition of claim 7wherein said azeotrope-like mixture consists essentially of about 70 toabout 99.5 weight percent cis-1-chloro-3,3,3-trifluoropropene and about0.5 to about 30 weight percent isohexane.
 17. A composition comprising abinary azeotrope-like mixture consisting essentially of1-chloro-3,3,3-trifluoropropene and a halogenated hydrocarbon selectedfrom the group consisting of 1-chloropropane, 2-chloropropane,1,1,1,3,3-pentafluorobutane, and trans-1,2-dichloroethylene, providedthat if said halogenated hydrocarbon is trans-1,2-dichloroethylene andsaid 1-chloro-3,3,3-trifluoropropene istrans-1-chloro-3,3,3-trifluoropropene, then said azeotrope-like mixturehas a boiling point of about 17° C. to about 19° C. at a pressure ofabout 14.7 psia±0.5 psi.
 18. The composition of claim 17 wherein saidazeotrope-like mixture consists essentially of about 96 to about 99.9weight percent trans-1-chloro-3,3,3-trifluoropropene and about 0.1 toabout 4 weight percent 1-chloropropane.
 19. The composition of claim 17wherein said azeotrope-like mixture consists essentially of about 94 toabout 99.9 weight percent trans-1-chloro-3,3,3-trifluoropropene andabout 0.1 to about 6 weight percent 2-chloropropane.
 20. The compositionof claim 17 wherein said azeotrope-like mixture consists essentially ofabout 89 to about 99.9 weight percenttrans-1-chloro-3,3,3-trifluoropropene and about 0.1 to about 11 weightpercent 1,1,1,3,3-pentafluorobutane.
 21. The composition of claim 17wherein said azeotrope-like mixture consists essentially of about 42 toabout 99.9 weight percent cis-1-chloro-3,3,3-trifluoropropene and about0.1 to about 58 weight percent trans-1,2-dichloroethylene.
 22. Acomposition comprising a binary azeotrope-like mixture consistingessentially of trans-1-chloro-3,3,3-trifluoropropene and a secondcomponent selected from the group consisting of methylal and methylacetate, provided that said trans-1-chloro-3,3,3-trifluoropropene ispresent in an amount that is at least 90 weight percent of said mixture.23. The composition of claim 22 wherein said azeotrope-like mixtureconsists essentially of about 95 to about 99.9 weight percenttrans-1-chloro-3,3,3-trifluoropropene and about 0.1 to about 5 weightpercent methylal.
 24. The composition of claim 22 wherein saidazeotrope-like mixture consists essentially of about 90 to about 99.9weight percent trans-1-chloro-3,3,3-trifluoropropene and about 0.1 toabout 10 weight percent methyl acetate.
 25. A composition comprising aternary azeotrope-like mixture consisting essentially of about 80 toabout 99.90 wt. % trans-1-chloro-3,3,3-trifluoropropene, about 0.05 toabout 15 wt. % methanol, and about 0.05 to about 10 wt. %trans-1,2-dichloroethylene.
 26. A composition comprising a binaryazeotrope-like mixture consisting essentially oftrans-1-chloro-3,3,3-trifluoropropene and water.
 27. A compositioncomprising a binary azeotrope-like mixture consisting essentially ofcis-1-chloro-3,3,3-trifluoropropene and nitromethane.
 28. A compositioncomprising a binary azeotrope-like mixture consisting essentially oftrans-1-chloro-3,3,3-trifluoropropene and nitromethane.